WO2021044852A1 - ウレタン樹脂組成物、及び、透湿フィルム - Google Patents
ウレタン樹脂組成物、及び、透湿フィルム Download PDFInfo
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- WO2021044852A1 WO2021044852A1 PCT/JP2020/031386 JP2020031386W WO2021044852A1 WO 2021044852 A1 WO2021044852 A1 WO 2021044852A1 JP 2020031386 W JP2020031386 W JP 2020031386W WO 2021044852 A1 WO2021044852 A1 WO 2021044852A1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
- C08G18/4018—Mixtures of compounds of group C08G18/42 with compounds of group C08G18/48
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4236—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups
- C08G18/4238—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups derived from dicarboxylic acids and dialcohols
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/0838—Manufacture of polymers in the presence of non-reactive compounds
- C08G18/0842—Manufacture of polymers in the presence of non-reactive compounds in the presence of liquid diluents
- C08G18/0847—Manufacture of polymers in the presence of non-reactive compounds in the presence of liquid diluents in the presence of solvents for the polymers
- C08G18/0852—Manufacture of polymers in the presence of non-reactive compounds in the presence of liquid diluents in the presence of solvents for the polymers the solvents being organic
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
- C08G18/3206—Polyhydroxy compounds aliphatic
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4833—Polyethers containing oxyethylene units
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6633—Compounds of group C08G18/42
- C08G18/6637—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
- C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
- C08G18/7671—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups containing only one alkylene bisphenyl group
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
- C08G18/7692—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing at least one isocyanate or isothiocyanate group linked to an aromatic ring by means of an aliphatic group
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2375/04—Polyurethanes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2375/04—Polyurethanes
- C08J2375/06—Polyurethanes from polyesters
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2375/04—Polyurethanes
- C08J2375/08—Polyurethanes from polyethers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/16—Applications used for films
Definitions
- the present invention relates to a urethane resin composition and a moisture permeable film.
- Moisture-permeable and waterproof functional clothing that has both moisture permeability and waterproofness is a structure in which a moisture-permeable film is attached to a fabric with an adhesive, and the moisture-permeable film is made of urethane in terms of elasticity and processability. Resin is commonly used.
- the moisture permeable film for example, a wet film-forming film of urethane resin, a non-porous film of hydrophilic urethane resin, and the like have been used (see, for example, Patent Document 1).
- a wet film-forming film of urethane resin, a non-porous film of hydrophilic urethane resin, and the like have been used (see, for example, Patent Document 1).
- the attention to sustainable products aiming to break away from petroleum resources is increasing, and the needs for urethane resins based on petroleum raw materials are also increasing. It is increasing.
- An object to be solved by the present invention is to provide a urethane resin composition which uses a biomass raw material and has excellent moisture permeability and film strength.
- the present invention is a urethane resin composition containing a polyol (A) containing a polyol (a1) having an oxyethylene group and a urethane resin (X) containing polyisocyanate (B) as an essential raw material.
- A) further contains a polyester polyol (a2) made from a biomass-derived glycol (i) and a crystalline polybasic acid (ii), and the hydroxyl group equivalent of the polyol (A) is 400 to 600 g / eq.
- a urethane resin composition characterized by being in the range of.
- the present invention also provides a moisture permeable film characterized by being formed of the urethane resin composition.
- the urethane resin composition of the present invention uses a biomass raw material and is an environment-friendly material. Further, since the urethane resin composition of the present invention is excellent in moisture permeability and film strength, it can be particularly preferably used for producing a moisture permeable film.
- the urethane resin composition of the present invention is a urethane resin composition containing a polyol (A) containing a polyol (a1) having an oxyethylene group and a urethane resin (X) containing polyisocyanate (B) as an essential raw material.
- the polyol (A) further contains a polyester polyol (a2) made from a biomass-derived glycol (i) and a crystalline polybasic acid (ii), and has a hydroxyl group equivalent of the polyol (A). However, 400-600 g / eq. It is in the range of.
- the polyol (a1) having an oxyethylene group is an indispensable material for obtaining excellent moisture permeability.
- the polyol (a1) for example, a polyoxyethylene polyol, a polyoxyethylene polyoxypropylene polyol, a polyoxyethylene polyoxytetramethylene polyol, or the like can be used. These polyols may be used alone or in combination of two or more. Among these, it is preferable to use a polyoxyethylene polyol from the viewpoint that excellent moisture permeability can be easily obtained.
- the number average molecular weight of the polyol (a1) is preferably in the range of 800 to 50,000, more preferably in the range of 1,000 to 20,000, from the viewpoint of obtaining even more excellent moisture permeability and film strength. preferable.
- the number average molecular weight of the polyol (a1) indicates a value measured by a gel permeation chromatography (GPC) method.
- polyol (a1) those produced from biomass raw materials can also be used, but at present, those that are expensive and can be actually used are extremely limited. Therefore, it is necessary to increase the degree of biomass from raw materials other than this polyol (a1).
- the polyol (A) in addition to the polyol (a1), a polyester polyol (a2) made from biomass-derived glycol (i) and crystalline polybasic acid (ii) as raw materials. While increasing the degree of biomass by using, it has both excellent film strength.
- biomass-derived glycol (i) examples include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,10-decanediol, dimerdiol, and isosorbide. Can be used. These compounds may be used alone or in combination of two or more.
- ethylene glycol for example, one obtained from bioethanol obtained by a known method via ethylene can be used.
- 1,2-propanediol for example, one obtained by fermentation of saccharides; one obtained by high-temperature hydrogenation of glycerin produced as a by-product of biodiesel by a known method can be used. it can.
- 1,3-propadiol include those obtained by producing 3-hydroxypropionaldehyde from glycerol, glucose, and other sugars by a known fermentation method, and then further converting to 1,3-propanediol; glucose and other substances. Those obtained directly from sugars by a fermentation method can be used.
- Examples of the 1,4-butanediol include glucose obtained by a known fermentation method; obtained from 1,3-butadiene obtained by a fermentation method; succinic acid hydrogenated with a reduction catalyst. It is possible to use the obtained product.
- the 1,10-decanediol for example, one obtained by hydrogenating sebacic acid directly or after an esterification reaction can be used.
- the dimer diol one obtained by reducing dimer acid by a known method or the like can be used.
- As the isosorbide for example, one obtained by dehydrating and condensing sorbitol obtained from starch by a known method can be used.
- biomass-derived glycol (i) 1,3-propanediol and / or 1,4-butanediol are preferable, and 1,4-butanediol is preferable from the above-mentioned ones from the viewpoint of obtaining even more excellent film strength.
- 3-Propanediol is more preferred.
- crystalline diprotic acid (ii) for example, sebacic acid, succinic acid, 1,10-decanedicarboxylic acid, 1,12-dodecanedicarboxylic acid and the like can be used.
- these polybasic acids those derived from petroleum resources and those derived from biomass can be used. These compounds may be used alone or in combination of two or more. Among these, it is preferable to use a crystalline polybasic acid derived from biomass from the viewpoint that the degree of biomass can be increased.
- crystallization means that the peak of heat of crystallization or heat of fusion can be confirmed in DSC (differential scanning calorimetry) measurement based on JISK7121: 2012, and is referred to as "amorphous”. Indicates that the peak cannot be confirmed.
- sebacic acid for example, one obtained by a known cleavage reaction of a vegetable oil such as castor oil with a caustic alkali can be used.
- succinic acid for example, corn, sugar cane, cassava, sago palm and the like fermented by a known method can be used.
- 1,10-decandicarboxylic acid for example, one obtained by fermenting lauryl acid by a known method can be used.
- 1,12-dodecanedioic acid for example, myristic acid fermented by a known method can be used.
- crystalline polybasic acids sebacic acid derived from biomass, succinic acid, 1,10-decandicarboxylic acid, and 1
- a compound selected from the group consisting of 12-dodecanedicarboxylic acid is preferable, sebacic acid derived from biomass and / or succinic acid is more preferable, and sebacic acid derived from biomass is further preferable.
- the number average molecular weight of the polyester polyol (a2) is preferably in the range of 500 to 100,000, more preferably in the range of 700 to 50,000, and more preferably in the range of 800 to 10, from the viewpoint of obtaining even more excellent film strength.
- the range of 000 is more preferable.
- the number average molecular weight of the polyester polyol (a2) indicates a value measured by a gel permeation chromatography (GPC) method.
- a chain extender (a3) having a molecular weight in the range of 40 to 500 can be used as the polyol (A) from the viewpoint that even more excellent film strength can be obtained.
- the molecular weight of the chain extender (a3) indicates a value calculated from a chemical formula.
- chain extender (a3) examples include ethylene glycol, diamine glycol, triethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, hexamethylene glycol, and tri.
- Chain extenders with hydroxyl groups such as methylolpropane and glycerin; ethylenediamine, 1,2-propanediamine, 1,6-hexamethylenediamine, piperazin, 2-methylpiperazine, 2,5-dimethylpiperazine, isophoronediamine, 4,4 '-Dicyclohexylmethanediamine, 3,3'-dimethyl-4,4'-dicyclohexylmethanediamine, 1,2-cyclohexanediamine, 1,4-cyclohexanediamine, aminoethylethanolamine, hydrazine, diethylenetriamine, triethylenetetramine, etc.
- a chain extender having an amino group can be used.
- chain extenders (a3) those derived from petroleum resources and those derived from biomass can be used. These chain extenders may be used alone or in combination of two or more.
- polyol (A) in addition to the above (a1), (a2), and (a3), other polyols may be used in combination as long as the effects of the present invention are not impaired.
- a polyester polyol derived from petroleum a polyether polyol other than the above (a1), a polycarbonate polyol, a polyacrylic polyol, a polybutadiene polyol, or the like can be used. These polyols may be used alone or in combination of two or more.
- the hydroxyl group equivalent of the polyol (A) is 400 to 600 g / eq. It is essential that it is in the range of.
- the hydroxyl group equivalent indicates the molecular weight per hydroxyl group, and the range concerned is a range in which the polyol (A) is relatively high among the raw materials constituting the urethane resin (X), and the urethane resin (X) has a relatively high range. Indicates that there are relatively few hard segments.
- the amount of the polyol (a1) having an oxyethylene group used is preferably in the range of 10 to 30% by mass, more preferably in the range of 10 to 20% by mass, based on the total amount of the raw materials constituting the urethane resin (X).
- the amount of the polyester polyol (a2) used is preferably in the range of 40 to 70% by mass, more preferably in the range of 50 to 60% by mass, based on the total amount of the raw materials constituting the urethane resin (X).
- the amount used is preferably in the range of 2 to 6% by mass, more preferably in the range of 2 to 4% by mass, based on the total amount of the raw materials constituting the urethane resin (X).
- polyisocyanate (B) examples include aromatic polyisocyanates such as polymethylene polyphenyl polyisocyanate, diphenylmethane diisocyanate, carbodiimide-modified diphenylmethane diisocyanate isocyanate, xylylene diisocyanate, phenylenedi isocyanate, tolylene diisocyanate, and naphthalene diisocyanate; hexamethylene diisocyanate and cyclohexane.
- aromatic polyisocyanates such as polymethylene polyphenyl polyisocyanate, diphenylmethane diisocyanate, carbodiimide-modified diphenylmethane diisocyanate isocyanate, xylylene diisocyanate, phenylenedi isocyanate, tolylene diisocyanate, and naphthalene diisocyanate; hexamethylene diisocyanate and cyclohexan
- An aliphatic or alicyclic polyisocyanate such as diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, or tetramethylxylylene diisocyanate can be used.
- these polyisocyanates (B) those derived from petroleum resources and those derived from biomass can be used. These polyisocyanates may be used alone or in combination of two or more. Among these, aromatic polyisocyanates are preferably used, and diphenylmethane diisocyanates are more preferable, from the viewpoint of obtaining even more excellent film strength and moisture permeability.
- the amount of the polyisocyanate (B) used is preferably in the range of 15 to 25% by mass, more preferably in the range of 17 to 23% by mass, based on the total amount of the raw materials constituting the urethane resin (X).
- Examples of the method for producing the urethane resin (X) include a method in which the polyol (A) and the polyisocyanate (C) are collectively charged and reacted, and the reaction is, for example, 30 to 30 to. It is preferably carried out at a temperature of 100 ° C. for 3 to 10 hours. Further, the reaction may be carried out in a solvent described later.
- the molar ratio of the hydroxyl group of the polyol (A) to the isocyanate group of the polyisocyanate (B) [(isocyanate group) / (hydroxyl group and amino group)] is in the range of 0.6 to 2. Is preferable, and the range is more preferably 0.8 to 1.2.
- the weight average molecular weight of the urethane resin (X) is preferably in the range of 10,000 to 1,000,000, more preferably in the range of 30,000 to 500,000, from the viewpoint of obtaining even more excellent film strength. It is preferable, and the range of 50,000 to 100,000 is more preferable.
- the weight average molecular weight of the urethane resin (X) indicates a value measured by a gel permeation chromatography (GPC) method.
- the biomass degree of the urethane resin (X) is preferably 40% or more, more preferably 50 to 60%, from the viewpoint of excellent moisture permeability and compatibility with film strength.
- the degree of biomass of the urethane resin (X) indicates the ratio of the total weight of the biomass-derived raw materials used in producing the urethane resin (X) to the total weight of the urethane resin (X).
- the urethane resin composition contains the urethane resin (X) as an essential component, but may contain other components if necessary.
- Examples of the other components include solvents, pigments, flame retardants, plasticizers, softeners, stabilizers, waxes, defoamers, dispersants, penetrants, surfactants, fillers, fungicides, antibacterial agents, and the like.
- solvents solvents, pigments, flame retardants, plasticizers, softeners, stabilizers, waxes, defoamers, dispersants, penetrants, surfactants, fillers, fungicides, antibacterial agents, and the like.
- Ultraviolet absorbers, antioxidants, weather stabilizers, fluorescent whitening agents, antioxidants, thickeners and the like can be used. These components may be used alone or in combination of two or more.
- the solvent examples include water, N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, methylethylketone, methyl-n-propylketone, acetone, methylisobutylketone and other ketone solvents; Ester solvents such as methyl formate, ethyl formate, propyl formate, methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, isobutyl acetate, secondary butyl acetate; alcohol solvents such as methanol, ethanol, isopropyl alcohol and butanol are used. be able to. These solvents may be used alone or in combination of two or more.
- the content of the solvent is preferably in the range of 10 to 90% by mass, more preferably in the range of 50 to 80% by mass in the urethane resin composition from the viewpoint of workability, viscosity, and film strength.
- the urethane resin composition of the present invention uses a biomass raw material and is an environment-friendly material. Further, since the urethane resin composition of the present invention is excellent in moisture permeability and film strength, it can be particularly preferably used for producing a moisture permeable film.
- the moisture permeable film is formed of the urethane resin composition.
- Examples of the method for forming the moisture-permeable film include a method in which the urethane resin composition is applied onto a paper pattern and dried at a temperature in the range of 40 to 150 ° C. for, for example, 1 to 30 minutes.
- Examples of the method of applying the composition to the surface of the base material include a gravure coater method, a knife coater method, a pipe coater method, a comma coater method and the like.
- the thickness of the moisture permeable film can be determined according to the intended use, and is, for example, in the range of 0.01 to 10 mm. ..
- the moisture-permeable film of the present invention is used for producing a moisture-permeable and waterproof functional garment, as a method for producing the moisture-permeable and waterproof functional garment, for example, the moisture-permeable film is used as a cloth using a known adhesive.
- the fabric include chemical fibers such as polyester fibers, nylon fibers, acrylic fibers, polyurethane fibers, acetate fibers, rayon fibers, and polylactic acid fibers; cotton, linen, silk, wool, and blended fibers thereof.
- the urethane resin composition is directly applied onto the dough, a dried product of the urethane resin composition is formed inside the dough. In the present invention, this is the case.
- the aspect is also called a film.
- Example 1 A four-necked flask equipped with a thermometer, agitator, an inert gas inlet and a reflux condenser is filled with a biomass polyester polyol (sebacic acid (“sebacic acid” manufactured by Toyokuni Oil Co., Ltd., hereinafter abbreviated as “bioSEBA”). And 1,3-propanediol (“SUSTERRA propanediol” manufactured by Dupont, hereinafter abbreviated as “bioPD”), number average molecular weight; 2,000, hereinafter abbreviated as “bioPEs (1)”.
- bioSEBA biomass polyester polyol
- bioPD 1,3-propanediol
- bioPD 1,3-propanediol
- bioPEs (1) number average molecular weight
- Example 2 instead of the bio-PEs (1), a reaction product of a biomass polyester polyol (bio-SEBA and 1,4-butanediol (“Bio-BDO” manufactured by Jenomatica, hereinafter abbreviated as “bio-BG”), number average molecular weight.
- Bio-BG biomass polyester polyol
- a urethane resin composition having a viscosity at 25 ° C. of 30,000 mPa ⁇ s was prepared in the same manner as in Example 1 except that 2,000 (hereinafter abbreviated as “bioPEs (2)”) was used. Obtained.
- Example 3 In a four-necked flask equipped with a thermometer, a stirrer, an inert gas inlet and a reflux condenser, 120 parts by mass of "Bio-PEs (1)", petroleum-based polyethylene glycol (number average molecular weight; 8,000, hereinafter “PEG” (2) ”is abbreviated.) 60 parts by mass was charged, dried under reduced pressure at 110 ° C., and dehydrated until the water content became 0.05% by mass or less.
- Bio-PEs (1) petroleum-based polyethylene glycol (number average molecular weight; 8,000, hereinafter "PEG” (2) ”is abbreviated.)
- EG petroleum-based ethylene glycol
- MDI diphenylmethane diisocyanate
- Measuring device High-speed GPC device ("HLC-8220GPC” manufactured by Tosoh Corporation) Column: The following columns manufactured by Tosoh Corporation were connected in series and used. "TSKgel G5000" (7.8 mm ID x 30 cm) x 1 "TSKgel G4000” (7.8 mm ID x 30 cm) x 1 "TSKgel G3000" (7.8 mm ID x 30 cm) x 1 This "TSKgel G2000" (7.8 mm ID x 30 cm) x 1 Detector: RI (Differential Refractometer) Column temperature: 40 ° C Eluent: tetrahydrofuran (THF) Flow velocity: 1.0 mL / min Injection volume: 100 ⁇ L (tetrahydrofuran solution with a sample concentration of 0.4% by mass) Standard sample: A calibration curve was prepared using the following standard polystyrene.
- the moisture permeability (g / m 2 / 24h) of each of the obtained moisture-permeable films was measured according to the B-1 method (potassium acetate method) of JIS L1099: 2012, and evaluated as follows. "T”: 20,000 g / m 2 / 24h or more. "F”: less than 20,000 g / m 2 / 24h.
- the urethane resin composition of the present invention uses a biomass raw material and has excellent moisture permeability and film strength.
- Comparative Example 1 the hydroxyl group equivalent of the polyol (A) was less than the range specified in the present invention, but the moisture permeability was poor.
- Comparative Example 2 was an embodiment in which castor oil polyol was used instead of polyester polyol (a2), but the film strength was poor.
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Abstract
Description
。
温度計、撹拌機、不活性ガス導入口および還流冷却器を備えた四口フラスコに、バイオマスポリエステルポリオール(セバシン酸(豊国製油株式会社製「セバシン酸」、以下「バイオSEBA」と略記する。)と1,3-プロパンジオール(Dupont社製「SUSTERRA プロパンジオール」、以下「バイオPD」と略記する。)との反応物、数平均分子量;2,000、以下「バイオPEs(1)」と略記する。)120質量部、石油系ポリエチレングリコール(数平均分子量;2,000、以下「PEG(1)」60質量部と略記する。)を仕込み、110℃にて減圧乾燥して、水分量が0.05質量%以下となるまで脱水した。次いで、石油系エチレングリコール(以下「EG」と略記する。)6質量部、ジメチルホルムアミド410質量部を加え、60℃に冷却後、ジフェニルメタンジイソシアネート(以下「MDI」と略記する。)47質量部加え、80℃まで昇温し、4時間反応後、バイオPDを0.5質量部、メチルエチルケトン130質量部を加え、反応を停止し、25℃での粘度が、30,000mPa・sのウレタン樹脂組成物を得た。
前記バイオPEs(1)に代え、バイオマスポリエステルポリオール(バイオSEBAと1,4-ブタンジオール(Jenomatica社製「Bio-BDO」、以下「バイオBG」と略記する。)との反応物、数平均分子量;2,000、以下「バイオPEs(2)」と略記する。)を用いた以外は、実施例1と同様にして、25℃での粘度が、30,000mPa・sのウレタン樹脂組成物を得た。
温度計、撹拌機、不活性ガス導入口および還流冷却器を備えた四口フラスコに、「バイオPEs(1)」120質量部、石油系ポリエチレングリコール(数平均分子量;8,000、以下「PEG(2)」と略記する。)60質量部を仕込み、110℃にて減圧乾燥して、水分量が0.05質量%以下となるまで脱水した。次いで、石油系エチレングリコール(以下「EG」と略記する。)7.5質量部、ジメチルホルムアミド410質量部を加え、60℃に冷却後、ジフェニルメタンジイソシアネート(以下「MDI」と略記する。)47質量部加え、80℃まで昇温し、4時間反応後、バイオPDを0.5質量部、メチルエチルケトン130質量部を加え、反応を停止し、25℃での粘度が、30,000mPa・sのウレタン樹脂組成物を得た。
温度計、撹拌機、不活性ガス導入口および還流冷却器を備えた四口フラスコに、バイオPEs(1)120質量部、PEG(1)60質量部を仕込み、110℃にて減圧乾燥して、水分量が0.05質量%以下となるまで脱水した。次いで、EG19質量部、ジメチルホルムアミド530質量部を加え、60℃に冷却後、MDI99質量部加え、80℃まで昇温し、4時間反応後、バイオPDを0.5質量部、メチルエチルケトン165質量部を加え、反応を停止し、25℃での粘度が、30,000mPa・sのウレタン樹脂組成物を得た。
温度計、撹拌機、不活性ガス導入口および還流冷却器を備えた四口フラスコに、ひまし油ジオール(伊藤製油株式会社製「PH-5002」、数平均分子量;2,600)120質量部、PEG(1)60質量部を仕込み、110℃にて減圧乾燥して、水分量が0.05質量%以下となるまで脱水した。次いで、EG6.8質量部、ジメチルホルムアミド410質量部を加え、60℃に冷却後、MDI47質量部加え、80℃まで昇温し、4時間反応後、バイオPDを0.5質量部、メチルエチルケトン130質量部を加え、反応を停止し、25℃での粘度が、30,000mPa・sのウレタン樹脂組成物を得た。
実施例及び比較例で用いたポリオール等の数平均分子量、ウレタン樹脂(X)の重量平均分子量は、ゲル・パーミエーション・クロマトグラフィー(GPC)法により、下記の条件で測定した値を示す。
カラム:東ソー株式会社製の下記のカラムを直列に接続して使用した。
「TSKgel G5000」(7.8mmI.D.×30cm)×1本
「TSKgel G4000」(7.8mmI.D.×30cm)×1本
「TSKgel G3000」(7.8mmI.D.×30cm)×1本
「TSKgel G2000」(7.8mmI.D.×30cm)×1本
検出器:RI(示差屈折計)
カラム温度:40℃
溶離液:テトラヒドロフラン(THF)
流速:1.0mL/分
注入量:100μL(試料濃度0.4質量%のテトラヒドロフラン溶液)
標準試料:下記の標準ポリスチレンを用いて検量線を作成した。
東ソー株式会社製「TSKgel 標準ポリスチレン A-500」
東ソー株式会社製「TSKgel 標準ポリスチレン A-1000」
東ソー株式会社製「TSKgel 標準ポリスチレン A-2500」
東ソー株式会社製「TSKgel 標準ポリスチレン A-5000」
東ソー株式会社製「TSKgel 標準ポリスチレン F-1」
東ソー株式会社製「TSKgel 標準ポリスチレン F-2」
東ソー株式会社製「TSKgel 標準ポリスチレン F-4」
東ソー株式会社製「TSKgel 標準ポリスチレン F-10」
東ソー株式会社製「TSKgel 標準ポリスチレン F-20」
東ソー株式会社製「TSKgel 標準ポリスチレン F-40」
東ソー株式会社製「TSKgel 標準ポリスチレン F-80」
東ソー株式会社製「TSKgel 標準ポリスチレン F-128」
東ソー株式会社製「TSKgel 標準ポリスチレン F-288」
東ソー株式会社製「TSKgel 標準ポリスチレン F-550」
実施例、及び、比較例で得られたウレタン樹脂組成物を、ジメチルホルムアミド30質量部で希釈した配合液を、離型紙上に塗布し、70℃、120℃でそれぞれ乾燥し、透湿フィルムを得た。
得られたそれぞれの透湿フィルムについて、JISL1099:2012のB-1法(酢酸カリウム法)に準拠して透湿度(g/m2/24h)を測定し、以下のように評価した。
「T」:20,000g/m2/24h以上である。
「F」:20,000g/m2/24h未満である。
得られたそれぞれの透湿フィルムを、幅5mm、長さ50mmの短冊状に裁断し、引張試験機「オートグラフAG-I」(株式会社島津製作所製)を用いて、温度23℃の雰囲気下で、クロスヘッドスピード10mm/秒の条件で引張り、試験片の100%モジュラス(MPa)を測定した。この時のチャック間距離は40mmとした。得られた100%モジュラス値から、フィルム強度を以下のように評価した。
「T」:2MPa以上である。
「F」:2MPa未満である。
Claims (6)
- オキシエチレン基を有するポリオール(a1)を含むポリオール(A)、及び、ポリイソシアネート(B)を必須原料とするウレタン樹脂(X)を含有するウレタン樹脂組成物であって、
前記ポリオール(A)が、更に、バイオマス由来のグリコール(i)と、結晶性多塩基酸(ii)とを原料とするポリエステルポリオール(a2)を含有し、
前記ポリオール(A)の水酸基当量が、400~600g/eq.の範囲であることを特徴とするウレタン樹脂組成物。 - 前記バイオマス由来のグリコール(i)が、1,3-プロパンジオール、及び/又は、1,4-ブタンジオールである請求項1記載のウレタン樹脂組成物。
- 前記結晶性多塩基酸(ii)が、バイオマス由来のものである請求項1又は2記載のウレタン樹脂組成物。
- 前記バイオマス由来の結晶性多塩基酸が、セバシン酸、コハク酸、1,10-デカンジカルボン酸、及び、1,12-ドデカンジカルボン酸からなる群より選ばれる1種以上の化合物である請求項3記載のウレタン樹脂組成物。
- バイオマス度が、50%以上である請求項1~4のいずれか1項記載のウレタン樹脂組成物。
- 請求項1~5のいずれか1項記載のウレタン樹脂組成物により形成されたことを特徴とする透湿フィルム。
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US17/639,590 US11897994B2 (en) | 2019-09-06 | 2020-08-20 | Urethane resin composition and moisture-permeable film |
CN202080056643.1A CN114206966A (zh) | 2019-09-06 | 2020-08-20 | 氨基甲酸酯树脂组合物及透湿膜 |
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