JP2024085529A - Urethane resin composition and fiber laminate - Google Patents

Abstract

To provide a urethane resin composition that offers superior moisture permeability, water swelling resistance, light resistance and solution stability, and a fiber laminate with a layer composed of the urethane resin composition.SOLUTION: A urethane resin composition includes a urethane resin (A), which includes a polyol compound (a1) and a polyisocyanate compound (a2) as essential raw materials, and an organic solvent (B). The polyol compound (a1) includes polyester polyol (a1-1) and polyethylene glycol (a1-2). The polyester polyol (a1-1) includes a glycol compound including diethylene glycol and sebacic acid as essential raw materials.SELECTED DRAWING: None

Description

The present invention relates to a urethane resin composition and a fiber laminate.

Urethane resin compositions can form films with good flexibility and strength, and have been used in a variety of applications, including as adhesives, coating agents, and molding materials. In particular, urethane resin compositions, taking advantage of their good soft feel, are ideally used in the surface layer of synthetic leather and artificial leather, as well as the surface layer of moisture-permeable waterproof fabrics.

The moisture-permeable waterproof fabric is a structure in which a moisture-permeable film is applied onto a substrate, and examples of urethane resin compositions used for this purpose include polyurethane resins whose constituent monomers are a polymer polyol containing a polyoxyalkylene diol and a polyester diol, and an organic polyisocyanate, and in which the solubility parameter of the polyester diol obtained by removing the hydroxyl groups at both ends from the polyester diol is 9.00 to 9.70, and the content of oxyethylene groups based on the weight of the polyurethane resin is 10 to 60% by weight (see Patent Document 1). However, these polyurethane resins have insufficient resistance to swelling in water, and problems such as poor light resistance due to ether bonds and reduced solution stability due to high crystallinity have been reported.

Therefore, there was a demand for a material that has even better moisture permeability, as well as excellent resistance to swelling in water, light resistance, and solution stability.

JP 2018-65940 A

The problem that the present invention aims to solve is to provide a urethane resin composition having excellent moisture permeability, water swelling resistance, light resistance and solution stability, and a fiber laminate having a layer formed from the urethane resin composition.

As a result of intensive research into solving the above problems, the inventors discovered that the above problems could be solved by using a urethane resin composition containing a urethane resin made from a specific polyol compound and a polyisocyanate compound as essential raw materials, and an organic solvent, and thus completed the present invention.

That is, the present invention relates to a urethane resin composition containing a urethane resin (A) whose essential raw materials are a polyol compound (a1) and a polyisocyanate compound (a2), and an organic solvent (B), characterized in that the polyol compound (a1) contains a polyester polyol (a1-1) and a polyethylene glycol (a1-2), and the polyester polyol (a1-1) contains a glycol compound containing diethylene glycol and sebacic acid as essential raw materials.

The urethane resin composition of the present invention is able to impart moisture permeability derived from diethylene glycol, water resistance derived from sebacic acid, and light resistance derived from ester groups, in addition to moisture permeability derived from diethylene glycol, by combining polyethylene glycol with a polyester polyol composed of diethylene glycol and sebacic acid. Furthermore, because diethylene glycol, which has a high affinity for polyethylene glycol, is incorporated into the polyester polyol structure, the affinity between the polyols is increased, and excellent solution stability can be achieved.

The urethane resin composition of the present invention has excellent moisture permeability, water swelling resistance, light resistance and solution stability, and can therefore be suitably used as a surface layer for synthetic leather and artificial leather.

The urethane resin composition of the present invention is characterized by containing a urethane resin (A) and an organic solvent (B).

The urethane resin (A) is made of polyol compound (a1) and polyisocyanate compound (a2) as essential raw materials.

The polyol compound (a1) used contains polyester polyol (a1-1) and polyethylene glycol (a1-2).

The polyester polyol (a1-1) used is one that uses a glycol compound and sebacic acid as essential raw materials.

As the glycol compound, diethylene glycol is used as an essential component. The amount of diethylene glycol used is preferably in the range of 10 to 100% by mass, more preferably in the range of 30 to 100% by mass, in the glycol compound.

Other glycol compounds may be used as the glycol compound if necessary. Examples of the other glycol compounds include ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,3-butanediol, 1,2-butanediol, 2-methyl-1,3-propanediol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, 1,5-hexanediol, 3-methyl-1,5-pentanediol, 2-methyl-1,8-octanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,8-nonanediol, 2-ethyl-2-butyl-1,3-propanediol, 1,12-dodecanediol, 1,4-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, trimethylolpropane, trimethylolethane, glycerin, ε-caprolactone, and neopentyl glycol. These other glycol compounds can be used alone or in combination of two or more.

As the glycol compound, a biomass-derived glycol compound (hereinafter sometimes referred to as a "bio-based glycol compound") can be used because it can reduce the environmental load. In the present invention, "bio-based" refers to a compound produced from plant raw materials such as sugar cane, corn, and castor oil.

Examples of the bio-based glycol compounds include bio-based ethylene glycol, bio-based diethylene glycol, and bio-based 1,3-propanediol. These bio-based glycol compounds can be used alone or in combination of two or more. Among these, bio-based diethylene glycol is preferred because it can reduce the environmental load and can provide a urethane resin composition having excellent moisture permeability, water swelling resistance, light resistance, and solution stability.

The bio-based diethylene glycol may be, for example, one obtained by a known method using molasses such as that from sugar cane as a raw material, and a commercially available product may be, for example, "Bio DEG" manufactured by India Glycols.

As the sebacic acid, biomass-derived sebacic acid (hereinafter sometimes referred to as "bio-based sebacic acid") can be used because it reduces the environmental impact.

The bio-based sebacic acid may be, for example, one obtained by a known cleavage reaction of vegetable oils such as castor oil with caustic alkali, and a commercially available product is, for example, "Bio Seb" manufactured by Toyokuni Oil Mills Co., Ltd.

As the polyester polyol (a1-1), if necessary, a polybasic acid other than the sebacic acid can also be used as a raw material.

Examples of the polybasic acid include succinic acid, adipic acid, azelaic acid, dodecanedicarboxylic acid, maleic anhydride, fumaric acid, 1,3-cyclopentanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, and anhydrides of these acids. These polybasic acids can be used alone or in combination of two or more. In addition, polybasic acids derived from biomass (hereinafter sometimes referred to as "bio-based polybasic acids") can also be used because they reduce the environmental load.

Examples of the biobased polybasic acid include biobased succinic acid, biobased dimer acid, and biobased 2,5-furandicarboxylic acid. These biobased polybasic acids can be used alone or in combination of two or more.

Examples of bio-based succinic acid include those obtained by fermenting corn, sugar cane, cassava, sago palm, etc., using known methods.

The bio-based dimer acid may be, for example, an acid obtained by dimerizing unsaturated fatty acids of natural oils and fats derived from plants using a known method.

Examples of the bio-based 2,5-furandicarboxylic acid include those made from fructose as a raw material, and those obtained by a known method using furancarboxylic acid, a furfural derivative, and carbon dioxide.

In the present invention, polyester polyols obtained by using biomass-derived compounds for either or both of the glycol compound and the sebacic acid may be referred to as "bio-based polyester polyols."

The method for producing the polyester polyol (a1-1) is not particularly limited, but may be, for example, a method in which the glycol compound and the sebacic acid are subjected to an esterification reaction.

The number average molecular weight of the polyester polyol (a1-1) is preferably in the range of 500 to 20,000, and more preferably in the range of 1,000 to 8,000, since a urethane resin composition having excellent moisture permeability, water swelling resistance, light resistance, and solution stability can be obtained. In the present invention, the number average molecular weight indicates a value measured by gel permeation chromatography (GPC).

Examples of the polyethylene glycol (a1-2) include "PEG#600", "PEG#1000", "PEG#1500", "PEG#2000", "PEG#4000", "PEG#6000", "PEG#11000", and "PEG#20000" manufactured by NOF Corporation, and "ECO RENEX PEG 600-SS (AP)" manufactured by CRODA. These polyethylene glycols can be used alone or in combination of two or more kinds.

In addition, as the polyethylene glycol (a1-2), biomass-derived polyethylene glycol (hereinafter, sometimes referred to as "bio-based polyethylene glycol") can be used because it can reduce the environmental load. Examples of the bio-based polyethylene glycol include commercially available products manufactured by CRODA.

The mass ratio [(a1-1)/(a1-2)] of the polyester polyol (a1-1) to the polyethylene glycol (a1-2) is preferably in the range of 10/90 to 90/10, more preferably 50/50 to 90/10, and even more preferably 60/40 to 80/20, since a urethane resin composition having excellent moisture permeability, water swelling resistance, light resistance, and solution stability can be obtained.

As the polyol compound (a1), if necessary, polyol compounds other than the polyester polyol (a1-1) and the polyethylene glycol (a1-2) (hereinafter abbreviated as "other polyol compounds") can also be used.

Examples of the other polyol compounds include polycarbonate diols, polyether polyols, polybutadiene polyols, etc. These polyol compounds can be used alone or in combination of two or more kinds.

The number average molecular weight of the other polyol compounds is preferably in the range of 200 to 1,000,000, and more preferably in the range of 300 to 500,000, since this provides a urethane resin composition with excellent moisture permeability, water swelling resistance, light resistance, and solution stability.

The content of the other polyol compounds in the polyol compound (a1) is preferably in the range of 0 to 90% by mass.

Examples of the polyisocyanate compound (a2) include aromatic polyisocyanates such as phenylene diisocyanate, toluene diisocyanate, diphenylmethane diisocyanate, xylylene diisocyanate, naphthalene diisocyanate, polymethylene polyphenyl polyisocyanate, and carbodiimidized diphenylmethane polyisocyanate; aliphatic polyisocyanates such as hexamethylene diisocyanate, lysine diisocyanate, cyclohexane diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, dimer acid diisocyanate, and norbornene diisocyanate; alicyclic diisocyanates such as norbornane diisocyanate, isophorone diisocyanate, hydrogenated xylylene diisocyanate, and hydrogenated diphenylmethane diisocyanate. These polyisocyanates can be used alone or in combination of two or more. Among these, diphenylmethane diisocyanate is preferred because it gives a urethane resin composition with excellent moisture permeability, water swelling resistance, light resistance, and solution stability.

The amount of the polyisocyanate compound (a2) used is preferably in the range of 10 to 60% by mass, more preferably 10 to 55% by mass, and even more preferably 15 to 45% by mass, of the total mass of the raw materials of the urethane resin (A), since a urethane resin composition having excellent moisture permeability, water swelling resistance, light resistance, and solution stability can be obtained.

The urethane resin (A) may contain, as necessary, a chain extender (a3) as a raw material in addition to the polyol compound (a1) and the polyisocyanate compound (a2).

Examples of the chain extender (a3) include chain extenders 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, and glycerin; and chain extenders having an amino group, such as ethylenediamine, 1,2-propanediamine, 1,6-hexamethylenediamine, piperazine, 2-methylpiperazine, 2,5-dimethylpiperazine, isophoronediamine, 4,4'-dicyclohexylmethanediamine, 3,3'-dimethyl-4,4'-dicyclohexylmethanediamine, 1,2-cyclohexanediamine, 1,4-cyclohexanediamine, aminoethylethanolamine, hydrazine, diethylenetriamine, and triethylenetetramine. These chain extenders can be used alone or in combination of two or more. Among these, chain extenders having hydroxyl groups are preferred because they provide a urethane resin composition with excellent moisture permeability, water swelling resistance, light resistance, and solution stability, and ethylene glycol, diethylene glycol, 1,3-propanediol, and 1,4-butanediol are more preferred. Bio-based ethylene glycol, bio-based 1,3-propanediol, and the like can also be used because they reduce the environmental impact.

The amount of the chain extender (a3) used is preferably in the range of 0.1 to 50% by mass, more preferably 1 to 30% by mass, of the total mass of the raw materials of the urethane resin (A), since a urethane resin composition having excellent moisture permeability, water swelling resistance, light resistance, and solution stability can be obtained.

The method for producing the urethane resin (A) is not particularly limited, but examples thereof include a method (1) in which raw materials including the polyol compound (a1) and the polyisocyanate compound (a2) are charged together and reacted in an organic solvent.

Examples of the organic solvent include ketone solvents such as methyl ethyl ketone, acetone, dimethylformamide, and methyl isobutyl ketone; cyclic ether solvents such as tetrahydrofuran and dioxolane; ester solvents such as methyl acetate, ethyl acetate, and butyl acetate; aromatic solvents such as toluene, xylene, and solvent naphtha; alicyclic solvents such as cyclohexane and methylcyclohexane; alcohol solvents such as carbitol, cellosolve, methanol, isopropanol, butanol, and propylene glycol monomethyl ether; glycol ether solvents such as alkylene glycol monoalkyl ether, dialkylene glycol monoalkyl ether, and dialkylene glycol monoalkyl ether acetate; methoxypropanol, cyclohexanone, methyl cellosolve, diethylene glycol monoethyl ether acetate, and propylene glycol monomethyl ether acetate. These organic solvents can be used alone or in combination of two or more.

The reaction temperature in method (1) is preferably in the range of 30 to 100°C, more preferably in the range of 70 to 90°C.

The reaction time in method (1) is preferably in the range of 3 to 10 hours, more preferably in the range of 4 to 10 hours.

The reaction of the polyol compound (a1) with the polyisocyanate compound (a2) in the method (1) produces a urethane resin composition having excellent moisture permeability, water swelling resistance, light resistance and solution stability, so the mass ratio [(a1)/(a2)] is preferably in the range of 85/15 to 65/35.

The number average molecular weight of the urethane resin (A) is preferably in the range of 5,000 to 1,000,000, and more preferably in the range of 10,000 to 500,000, since a urethane resin composition having excellent moisture permeability, water swelling resistance, light resistance, and solution stability can be obtained.

The content of the urethane resin (A) in the urethane resin composition is preferably in the range of 10 to 90% by mass, more preferably 15 to 80% by mass, since this results in a urethane resin composition with excellent moisture permeability, water swelling resistance, light resistance, and solution stability.

As the organic solvent (B), the same organic solvents as those exemplified above can be used, and the organic solvents can be used alone or in combination of two or more kinds.

From the viewpoints of workability and viscosity, the content of the organic solvent (B) in the urethane resin composition is preferably in the range of 20 to 90% by mass, and more preferably in the range of 40 to 80% by mass.

The method for producing the urethane resin composition of the present invention is not particularly limited, but may be, for example, a method in which the organic solvent (B) is added to the urethane resin (A) solution obtained by the method (1) in the above-mentioned method for producing the urethane resin (A). The organic solvent (B) may be the same as the organic solvent used in producing the urethane resin (A), or may be different, but it is preferable that they are the same.

In addition, the urethane resin composition of the present invention may contain, as necessary, for example, pigments, flame retardants, plasticizers, softeners, stabilizers, waxes, defoamers, dispersants, penetrants, surfactants, fillers, antifungal agents, antibacterial agents, UV absorbers, antioxidants, weathering stabilizers, fluorescent brighteners, antiaging agents, thickeners, etc. These may be used alone or in combination of two or more.

The moisture permeable film of the present invention is made of the urethane resin composition.

The method for producing the moisture-permeable film is not particularly limited, but examples include a method in which the urethane resin composition is applied to a substrate and dried at a temperature range of 40 to 150°C for 1 to 30 minutes.

Examples of the substrate include substrates made of nonwoven fabric, woven fabric, or knitted fabric; resin films; and paper.

Examples of materials constituting the substrate made of the nonwoven fabric, woven fabric, or knitted fabric include chemical fibers such as polyester fiber, nylon fiber, acrylic fiber, polyurethane fiber, acetate fiber, rayon fiber, and polylactic acid fiber; cotton, hemp, silk, wool, and blended fibers thereof. When a substrate made of a nonwoven fabric, woven fabric, or knitted fabric is used as the substrate, the inside of the substrate is permeated with the dried urethane resin composition, and in the present invention, such a form is also referred to as a film.

The surface of the substrate may be subjected to antistatic treatment, release treatment, water repellency, water absorption, antibacterial and deodorizing treatment, bacteriostatic treatment, ultraviolet blocking treatment, etc., as necessary.

Examples of methods for applying the urethane resin composition to the surface of the substrate include the gravure coater method, knife coater method, pipe coater method, and comma coater method.

The thickness of the moisture permeable film can be determined according to the intended use and is not particularly limited, but is, for example, in the range of 0.01 to 10 mm.

The fiber laminate of the present invention has a layer formed from the urethane resin composition and a fiber substrate.

Examples of the fiber substrate include nonwoven fabric, woven fabric, knitted fabric, etc.

Furthermore, examples of materials constituting the fiber substrate include polyester fibers, nylon fibers, acrylic fibers, acetate fibers, rayon fibers, polylactic acid fibers, cotton, hemp, silk, wool, and blends thereof.

The fiber laminate of the present invention may also have an adhesive layer, if necessary.

The adhesive layer may be, for example, a known adhesive.

Examples of known adhesives include solventless urethane resin compositions such as moisture-curing hot melt resins, water-based urethane resin compositions in which urethane resins are dispersed in water, water-based acrylic resin compositions in which acrylic resins are dispersed in water, solvent-based urethane resin compositions, and solvent-based acrylic resin compositions. These adhesives can be used alone or in combination of two or more types.

The fiber laminate of the present invention can be suitably used, for example, as moisture-permeable, waterproof fabrics for clothing, medical and sanitary purposes, and synthetic leather.

The method for producing the fiber laminate of the present invention is not particularly limited, but examples include a method in which a moisture-permeable film made of the urethane resin composition is adhered to a fiber substrate using a known adhesive; a method in which the urethane resin composition is directly applied to a fiber substrate and then dried, etc.

The present invention will be specifically described below with reference to examples and comparative examples, but the present invention is not limited to the examples given below.

The number average molecular weights of the polyol compounds used in the examples and comparative examples are values measured by gel permeation chromatography (GPC) under the following conditions.

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

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

(Synthesis Example 1: Synthesis of polyester polyol (1))
In a four-neck flask equipped with a thermometer, a stirrer, an inert gas inlet and a reflux condenser, 187 parts by mass of bio-based sebacic acid (Bio Seb) and 113 parts by mass of bio-based diethylene glycol (Bio DEG) were charged, and 0.01% of tetraisopropyl titanate was added as an esterification catalyst relative to the total amount charged, and the mixture was reacted at 220 ° C. for 15 hours to obtain polyester polyol (1). The acid value of this polyester polyol (1) was 0.54 mg KOH / g, and the hydroxyl value was 55.6 mg KOH / g. In the present invention, the acid value of the polyester polyol is a value measured in accordance with JIS K1557-5 (2007). The hydroxyl value of the polyester polyol is a value measured in accordance with JIS K0070 (1992).

(Synthesis Examples 2 to 5: Synthesis of polyester polyols (2) to (5))
Polyester polyols (2) to (5) were obtained in the same manner as in Synthesis Example 1 based on the raw materials and compounding ratios (unit: parts by mass) shown in Table 1.

The compositions of polyester polyols (1) to (5) obtained in the synthesis examples are shown in Table 1.

In Table 1, "Bio DEG" refers to bio-based diethylene glycol (manufactured by India Glycols).

In Table 1, "Bio 1,3-PDO" refers to bio-based 1,3-propanediol (manufactured by DuPont).

In Table 1, "Bio EG" refers to bio-based ethylene glycol (manufactured by India Glycols).

In Table 1, "EG" refers to ethylene glycol (manufactured by Mitsubishi Chemical Corporation).

In Table 1, "BG" refers to butanediol (manufactured by Mitsubishi Chemical Corporation).

In Table 1, "Bio Seb" refers to bio-based sebacic acid (manufactured by Toyokuni Oil Mills Co., Ltd.).

In Table 1, "DEG" refers to diethylene glycol (manufactured by Mitsubishi Chemical Corporation).

In Table 1, "AA" stands for adipic acid (manufactured by Asahi Kasei Corporation).

(Example 1: Preparation of urethane resin composition (1))
In a four-neck flask equipped with a stirrer, a reflux condenser, a thermometer, and a nitrogen blowing tube, 350 parts by mass of the polyester polyol (1) obtained in Synthesis Example 1, 100 parts by mass of polyethylene glycol ethylene glycol (NOF Corporation "PEG # 6000", number average molecular weight 8800, hereinafter abbreviated as "PEG (1)"), 18 parts by mass of ethylene glycol, and 1365 parts by mass of N,N-dimethylformamide were added and thoroughly stirred and mixed under nitrogen gas flow. After stirring and mixing, 117 parts by mass of diphenylmethane diisocyanate (hereinafter abbreviated as "MDI") was added and reacted at 80 ° C. for 3 hours to obtain a urethane resin composition (1). The solid content of this urethane resin composition (1) was 30 mass %, and the viscosity was 300 dPa · s. In addition, the bio ratio was 60%.

(Example 2: Preparation of urethane resin composition (2))
In a four-neck flask equipped with a stirrer, a reflux condenser, a thermometer, and a nitrogen inlet tube, 350 parts by mass of the polyester polyol (2) obtained in Synthesis Example 2, 100 parts by mass of PEG (1), 18 parts by mass of ethylene glycol, and 1365 parts by mass of N,N-dimethylformamide were added under a nitrogen stream and thoroughly stirred and mixed. After stirring and mixing, 117 parts by mass of MDI was added and reacted at 80°C for 3 hours to obtain a urethane resin composition (2). The solid content of this urethane resin composition (1) was 30% by mass, and the viscosity was 300 dPa·s. The bio ratio was 60%.

(Example 3: Preparation of urethane resin composition (3))
In a four-neck flask equipped with a stirrer, a reflux condenser, a thermometer, and a nitrogen inlet tube, 350 parts by mass of the polyester polyol (3) obtained in Synthesis Example 3, 100 parts by mass of PEG (1), 18 parts by mass of ethylene glycol, and 1365 parts by mass of N,N-dimethylformamide were added under a nitrogen stream and thoroughly stirred and mixed. After stirring and mixing, 117 parts by mass of MDI was added and reacted at 80°C for 3 hours to obtain a urethane resin composition (3). The solid content of this urethane resin composition (3) was 30% by mass, and the viscosity was 300 dPa·s. The bio ratio was 60%.

(Example 4: Preparation of urethane resin composition (4))
In a four-neck flask equipped with a stirrer, a reflux condenser, a thermometer, and a nitrogen blowing tube, 250 parts by mass of the polyester polyol (1) obtained in Synthesis Example 1, 100 parts by mass of the polyester polyol (4) obtained in Synthesis Example 4, 100 parts by mass of PEG (1), 18 parts by mass of ethylene glycol, and 1365 parts by mass of N,N-dimethylformamide were added under a nitrogen stream and thoroughly stirred and mixed. After stirring and mixing, 117 parts by mass of MDI was added and reacted at 80°C for 3 hours to obtain a urethane resin composition (4). The solid content of this urethane resin composition (4) was 30% by mass, and the viscosity was 300 dPa·s. The bio ratio was 60%.

(Example 5: Preparation of urethane resin composition (5))
In a four-neck flask equipped with a stirrer, a reflux condenser, a thermometer, and a nitrogen inlet tube, 350 parts by mass of the polyester polyol (1) obtained in Synthesis Example 1, 100 parts by mass of PEG (1), 18 parts by mass of bio-based ethylene glycol, and 1365 parts by mass of N,N-dimethylformamide were added under a nitrogen stream and thoroughly stirred and mixed. After stirring and mixing, 117 parts by mass of MDI was added and reacted at 80°C for 3 hours to obtain a urethane resin composition (5). The solid content of this urethane resin composition (5) was 30% by mass, and the viscosity was 300 dPa·s. The bio ratio was 63%.

(Example 6: Preparation of urethane resin composition (6))
In a four-neck flask equipped with a stirrer, a reflux condenser, a thermometer, and a nitrogen blowing tube, 350 parts by mass of the polyester polyol (1) obtained in Synthesis Example 1, 100 parts by mass of PEG (1), 31 parts by mass of bio-based diethylene glycol, and 1402 parts by mass of N,N-dimethylformamide were added under a nitrogen stream and thoroughly stirred and mixed. After stirring and mixing, 120 parts by mass of MDI was added and reacted at 80°C for 3 hours to obtain a urethane resin composition (6). The solid content of this urethane resin composition (6) was 30% by mass, and the viscosity was 300 dPa·s. The bio ratio was 63%.

(Example 7: Preparation of urethane resin composition (7))
In a four-neck flask equipped with a stirrer, a reflux condenser, a thermometer, and a nitrogen inlet tube, 350 parts by mass of the polyester polyol (1) obtained in Synthesis Example 1, 100 parts by mass of PEG (1), 22 parts by mass of bio-based 1,3-propanediol, and 1377 parts by mass of N,N-dimethylformamide were added under a nitrogen stream and thoroughly stirred and mixed. After stirring and mixing, 118 parts by mass of MDI was added and reacted at 80°C for 3 hours to obtain a urethane resin composition (7). The solid content of this urethane resin composition (7) was 30% by mass, and the viscosity was 300 dPa·s. The bio ratio was 63%.

(Example 8: Preparation of urethane resin composition (8))
In a four-neck flask equipped with a stirrer, a reflux condenser, a thermometer, and a nitrogen inlet tube, 350 parts by mass of the polyester polyol (1) obtained in Synthesis Example 1, 50 parts by mass of polyethylene glycol ethylene glycol (NOF Corporation "PEG # 11000", number average molecular weight 11000, hereinafter abbreviated as "PEG (2)"), 50 parts by mass of polyethylene glycol ethylene glycol (NOF Corporation "PEG # 2000", number average molecular weight 2000), 18 parts by mass of ethylene glycol, and 1365 parts by mass of N,N-dimethylformamide were added and thoroughly stirred and mixed under nitrogen flow. After stirring and mixing, 117 parts by mass of MDI was added and reacted at 80 ° C. for 3 hours to obtain a urethane resin composition (8). The solid content of this urethane resin composition (8) was 30% by mass, and the viscosity was 300 dPa · s. In addition, the bio ratio was 60%.

(Example 9: Preparation of urethane resin composition (9))
In a four-neck flask equipped with a stirrer, a reflux condenser, a thermometer, and a nitrogen inlet tube, 405 parts by mass of the polyester polyol (1) obtained in Synthesis Example 1, 45 parts by mass of PEG (2), 16 parts by mass of ethylene glycol, and 1363 parts by mass of N,N-dimethylformamide were added under a nitrogen stream and thoroughly stirred and mixed. After stirring and mixing, 118 parts by mass of MDI was added and reacted at 80°C for 3 hours to obtain a urethane resin composition (9). The solid content of this urethane resin composition (9) was 30% by mass, and the viscosity was 300 dPa·s. The bio ratio was 69%.

(Comparative Example 1: Preparation of urethane resin composition (R1))
In a four-neck flask equipped with a stirrer, a reflux condenser, a thermometer, and a nitrogen blowing tube, 300 parts by mass of PEG (1), 18 parts by mass of ethylene glycol, and 926 parts by mass of N,N-dimethylformamide were added under a nitrogen stream and thoroughly stirred and mixed. After stirring and mixing, 79 parts by mass of MDI was added and reacted at 80°C for 3 hours to obtain a urethane resin composition (R1). The solid content of this urethane resin composition (R1) was 30% by mass, and the viscosity was 350 dPa·s. The bio ratio was 0%.

(Comparative Example 2: Preparation of urethane resin composition (R2))
In a four-neck flask equipped with a stirrer, a reflux condenser, a thermometer, and a nitrogen blowing tube, 350 parts by mass of the polyester polyol (5) obtained in Synthesis Example 5, 100 parts by mass of PEG (1), 18 parts by mass of ethylene glycol, and 1365 parts by mass of N,N-dimethylformamide were added under a nitrogen stream and thoroughly stirred and mixed. After stirring and mixing, 117 parts by mass of MDI was added and reacted at 80°C for 3 hours to obtain a urethane resin composition (R2). The solid content of this urethane resin composition (R2) was 30% by mass, and the viscosity was 300 dPa·s. The bio ratio was 25%.

(Comparative Example 3: Preparation of urethane resin composition (R3))
In a four-neck flask equipped with a stirrer, a reflux condenser, a thermometer, and a nitrogen blowing tube, 350 parts by mass of the polyester polyol (4) obtained in Synthesis Example 4, 100 parts by mass of PEG (1), 18 parts by mass of ethylene glycol, and 1365 parts by mass of N,N-dimethylformamide were added under a nitrogen stream and thoroughly stirred and mixed. After stirring and mixing, 117 parts by mass of MDI was added and reacted at 80°C for 3 hours to obtain a urethane resin composition (R3). The solid content of this urethane resin composition (R3) was 30% by mass, and the viscosity was 300 dPa·s. The bio ratio was 60%.

The following evaluations were carried out using the urethane resin compositions (1) to (9) and (R1) to (R3) obtained in the above examples and comparative examples.

[Method for evaluating moisture permeability]
100 parts by mass of the urethane resin composition obtained in each Example and Comparative Example was diluted with 30 parts by mass of N,N-dimethylformamide, applied to release paper so that the thickness after drying was 15 μm, and dried using a dryer at 70° C. for 2 minutes and then at 120° C. for 2 minutes to obtain a moisture-permeable film. Next, the moisture permeability was measured using the obtained moisture-permeable film as a test piece by a method based on the A-1 method (calcium chloride method) described in JIS L1099 (2012), and the moisture permeability was evaluated according to the following evaluation criteria.

A: 4000 g/ ^m2 or more B: 3000 g/ ^m2 or more and less than 4000 g/ ^m2 C: Less than 3000 g/ ^m2

[Method for evaluating water swelling resistance]
100 parts by mass of the urethane resin composition obtained in each Example and Comparative Example was diluted with 30 parts by mass of N,N-dimethylformamide, applied to release paper so that the thickness after drying was 15 μm, dried at 70° C. for 2 minutes using a dryer, and then further dried at 120° C. for 2 minutes to obtain a moisture-permeable film, which was cut into 2 cm (vertical) x 5 cm (horizontal) to prepare a test piece. The obtained test piece was then immersed in ion-exchanged water at 25° C. for 1 hour, the horizontal length of the removed test piece was measured, and the swelling ratio (%) was calculated using the following formula (1), and the water swelling resistance was evaluated according to the following evaluation criteria.
Swelling ratio (%) = length of test piece after immersion (cm) - 5 (cm) / 5 (cm) x 100 (1)

A: Swelling rate less than 5% B: Swelling rate 5% or more

[Method for evaluating light resistance]
100 parts by mass of the urethane resin composition obtained in each Example and Comparative Example was diluted with 30 parts by mass of N,N-dimethylformamide, applied to a PET film so that the thickness after drying was 15 μm, and dried using a dryer at 70° C. for 2 minutes and then at 120° C. for 2 minutes to obtain a moisture-permeable film. The moisture-permeable film and the PET film were cut into 5 cm (length) x 5 cm (width) pieces to prepare test pieces. The obtained test pieces were irradiated for 100 hours at a black panel temperature of 63° C. using an ultraviolet fade meter ("U48HB" manufactured by Suga Test Instruments Co., Ltd.) (light source: ultraviolet carbon arc lamp, irradiance: 500 W/m ² ) and visually evaluated according to the following evaluation criteria.

A: No change in appearance.
B: Severe yellowing occurred.

[Method for evaluating solution stability]
The urethane resin compositions obtained in each of the Examples and Comparative Examples were allowed to stand at 5° C. for one week, and the solution state was observed and evaluated according to the following evaluation criteria.

A: High liquidity.
B: Low liquidity.
C: No fluidity. Precipitation was observed.

The compositions and evaluation results of the curable resin compositions (1) to (9) and (R1) to (R3) obtained in the above examples and comparative examples are shown in Tables 2 and 3.

Examples 1 to 9 shown in Table 2 are examples in which the urethane resin composition of the present invention was used. It was confirmed that these urethane resin compositions have excellent moisture permeability, resistance to swelling in water, light resistance, and solution stability.

On the other hand, Comparative Example 1 shown in Table 3 is an example of a urethane resin composition that does not use polyester polyol as a raw material for the urethane resin. It was confirmed that this urethane resin composition has extremely insufficient solution stability.

Comparative Example 2 shown in Table 3 is an example of a urethane resin composition in which sebacic acid is not used as a raw material in the polyester polyol, which is a raw material for urethane resin. It was confirmed that this urethane resin composition has extremely insufficient resistance to swelling in water.

Comparative Example 3 shown in Table 3 is an example of a urethane resin composition in which diethylene glycol is not used as a raw material in the polyester polyol, which is a raw material for urethane resin. It was confirmed that this urethane resin composition has extremely insufficient moisture permeability and solution stability.

Claims (10)

A urethane resin composition comprising a urethane resin (A) having a polyol compound (a1) and a polyisocyanate compound (a2) as essential raw materials, and an organic solvent (B),
the polyol compound (a1) contains a polyester polyol (a1-1) and a polyethylene glycol (a1-2);
A urethane resin composition, characterized in that the polyester polyol (a1-1) is made essentially from a glycol compound containing diethylene glycol and sebacic acid. The urethane resin composition according to claim 1, wherein the mass ratio [(a1-1)/(a1-2)] of the polyester polyol (a1-1) to the polyethylene glycol (a1-2) is in the range of 10/90 to 90/10. The urethane resin composition according to claim 1, wherein the polyester polyol (a1-1) is a bio-based polyester polyol. The urethane resin composition according to claim 1, wherein the diethylene glycol is bio-based diethylene glycol and the sebacic acid is bio-based sebacic acid. The urethane resin composition according to claim 4, wherein the content of the bio-based diethylene glycol in the glycol compound is in the range of 10 to 100% by mass. The urethane resin composition according to claim 1, wherein the polyisocyanate compound (a2) contains diphenylmethane diisocyanate. The urethane resin composition according to claim 1, wherein the urethane resin (A) further contains a chain extender (a3). The urethane resin composition according to claim 7, wherein the chain extender (a3) is at least one selected from the group consisting of ethylene glycol, diethylene glycol, 1,4-butanediol, and 1,3-propanediol. A moisture permeable film comprising the urethane resin composition according to any one of claims 1 to 8. A fiber laminate comprising a layer formed from the urethane resin composition according to any one of claims 1 to 8, and a fiber substrate.