WO2010137430A1 - 多孔体の製造方法ならびにそれによって得られた多孔体、積層体及び皮革様シート - Google Patents
多孔体の製造方法ならびにそれによって得られた多孔体、積層体及び皮革様シート Download PDFInfo
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- WO2010137430A1 WO2010137430A1 PCT/JP2010/057068 JP2010057068W WO2010137430A1 WO 2010137430 A1 WO2010137430 A1 WO 2010137430A1 JP 2010057068 W JP2010057068 W JP 2010057068W WO 2010137430 A1 WO2010137430 A1 WO 2010137430A1
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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
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/28—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a liquid phase from a macromolecular composition or article, e.g. drying of coagulum
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/40—Layered products comprising a layer of synthetic resin comprising polyurethanes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
- B32B5/18—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by features of a layer of foamed material
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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
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
- C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
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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
- C08G18/28—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
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene 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
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/0014—Use of organic additives
- C08J9/0023—Use of organic additives containing oxygen
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/07—Aldehydes; Ketones
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/10—Esters; Ether-esters
- C08K5/101—Esters; Ether-esters of monocarboxylic acids
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
- D06N3/12—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins
- D06N3/14—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins with 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
- C08J2375/08—Polyurethanes from polyethers
Definitions
- the present invention relates to a method for producing a porous body that can be used in various fields including, for example, leather-like sheets such as synthetic leather and artificial leather, and moisture-permeable and waterproof materials.
- the polyurethane resin composition can form a cured product having good flexibility and strength, it has been conventionally used in various applications such as adhesives, coating agents and molding materials.
- the polyurethane resin composition is suitably used for the production of porous bodies used for clothes, moisture-permeable waterproof materials, etc., including the intermediate layer and skin layer of leather-like sheets, taking advantage of its good flexible texture. Has been.
- a dry method and a wet method are known as a method for producing a porous body using the polyurethane resin composition.
- an organic medium having a boiling point of 120 ° C. or less and water solubility at 25 ° C. of 1 to 50 g, a polyurethane polymer having a predetermined amount of polyoxyethylene groups, and water There is known a method of forming a microporous sheet by contacting a base material coated with a water-in-oil mixed dispersion composed of, for example, with a specific coagulant for a short time (for example, Patent Document 1). reference.).
- the dry method is usually not a preferable method from the viewpoint of reducing the environmental load recently because it is difficult to recover the organic solvent used for the production of the porous body.
- the porous body obtained by the dry method is less likely to form pores on the surface, and when the polyurethane resin composition is applied to the substrate surface, skinning occurs, and the resulting porous body aggregates. Since things are likely to adhere, the production efficiency of the porous body may be reduced.
- a method for forming a porous body by a wet method for example, a resin compounded liquid containing a urethane resin for moisture-permeable waterproofing, dimethylformamide, a crosslinking agent, and the like is applied on a base material, and in a 10% aqueous solution of dimethylformamide
- a method of manufacturing a wet waterproof fabric that is immersed in and solidified see, for example, Patent Document 2).
- the wet method is a suitable method for producing a porous body because the organic solvent recovery means used for the production of the porous body is established to some extent and can prevent the occurrence of pinholes and skinning on the surface of the obtained porous body. It is implemented for various purposes.
- the porous body obtained by the wet method does not form a so-called communication hole in which a large number of holes communicate with each other like the porous body obtained by the dry method, and it is easy to form independent holes in which the holes are independent from each other. Therefore, there was a tendency to be inferior in terms of moisture permeability as compared with the porous body obtained by the dry method.
- the film thickness exceeds about 100 ⁇ m, such as a porous body forming an intermediate layer of a leather-like sheet, the porous body obtained by the wet method can impart a practically sufficient level of moisture permeability. There were cases where it was not possible.
- amide solvents such as dimethylformamide (DMF), which are frequently used as the organic solvent, are used for their adverse effects on living bodies and the environment. It tends to be strictly limited by law. For example, in Europe, the use of dimethylformamide is highly likely to be abolished by 2013.
- the problem to be solved by the present invention is that the use of an amide-based solvent such as dimethylformamide, which has a negative impact on the environment, and the like, and a very good permeability without generating aggregates by a wet method. It is to provide a method for producing a porous body having wettability.
- the present inventors selected various organic solvents and proceeded with investigations in order to find a solvent that can replace dimethylformamide conventionally used in wet methods.
- a solvent that can replace dimethylformamide conventionally used in wet methods Specifically, although an ester solvent such as ethyl acetate was examined, a porous body obtained by a wet method using such an ester solvent is difficult to uniformly form pores in the porous body. When the porous body is a thick film, the moisture permeability may be significantly reduced.
- the pores can still be uniformly formed in the porous body simply by using methyl ethyl ketone or the like instead of dimethylformamide.
- the porous body is a thick film, a practically sufficient level of moisture permeability may not be maintained.
- the present inventors employ a ketone solvent or an ester solvent such as methyl ethyl ketone as an alternative solvent for dimethylformamide, and form a desired porous body by a wet method even when such a solvent is used. We proceeded with examination.
- the present invention provides a urethane resin composition containing a urethane resin (A) having a polyoxyethylene structure and one or more organic solvents (B) selected from the group consisting of ketone solvents and ester solvents.
- a method for producing a porous body characterized in that the urethane resin (A) is wet-coagulated by applying or impregnating the substrate surface, and then bringing water or water vapor into contact with the coated surface or impregnated surface.
- the present invention relates to a porous body to be obtained.
- the present invention has a urethane resin (A) having a polyoxyethylene structure, one or more organic solvents (B) selected from the group consisting of ketone solvents and ester solvents, and a polyoxyethylene structure.
- a urethane resin composition containing no urethane resin (C) is applied or impregnated on the surface of the substrate, and then the urethane resin (A) and the above-mentioned resin are brought into contact with the coated surface or impregnated surface by water or steam.
- the present invention relates to a method for producing a porous body characterized by wet coagulation of a urethane resin (C) and a porous body obtained thereby.
- the “porous” of the porous body obtained in the present invention has a large number of pores that are naturally obtained by solidifying the urethane resin composition by a wet method, and has moisture permeability due to the pores. It means that.
- a porous body can be obtained by a wet method, without using the amide solvent which is anxious about the bad influence to an environment etc. Further, since the porous body has very excellent moisture permeability comparable to the porous body obtained by the dry method, for example, synthetic leather and artificial leather used for clothing, vehicle seats, furniture sheets, shoes, bags, etc.
- leather-like sheets such as surgical clothing and bed sheets, hygiene materials such as wind and waterproof sheets and anti-condensation sheets, packaging materials such as desiccants, dehumidifiers and fragrances, agricultural sheets, various separators
- the intermediate layer constituting the packing or the like can be used for various applications such as a skin layer.
- 6 is a cross-sectional photograph of a porous body obtained in Example 5 using a scanning electron microscope (SEM). 6 is a surface photograph of the porous body obtained in Example 5 by SEM. 4 is a cross-sectional photograph of the porous body obtained in Comparative Example 2 by SEM. 4 is a SEM surface photograph of the porous body obtained in Comparative Example 2.
- SEM scanning electron microscope
- the method for producing a porous body of the present invention includes a urethane resin (A) having a polyoxyethylene structure, one or more organic solvents (B) selected from the group consisting of ketone solvents and ester solvents, and as necessary.
- the urethane resin composition containing other additives is applied or impregnated on the surface of the base material, and then the urethane resin (A) is solidified by bringing water or water vapor into contact with the coated surface or impregnated surface. It is characterized by that.
- a urethane resin (A) having a polyoxyethylene structure is used as an essential component, and an organic solvent (B) using at least one selected from the group consisting of ketone solvents and ester solvents is used in combination.
- urethane resin having no polyoxyethylene structure is used instead of the urethane resin (A)
- a urethane resin having a polypropylene structure or the like is used, a communication hole is hardly formed. In some cases, a porous body having sufficient moisture permeability cannot be obtained.
- the method of using dimethylformamide instead of the organic solvent (B) is not preferable for reducing the environmental load, and it is easy to generate skin and aggregates on the surface of the porous body. Since it is difficult to form the film uniformly, it may not be possible to provide very good moisture permeability.
- any one having a polyoxyethylene structure in the molecule can be used, but the polyoxyethylene structure is used at the molecular end of the urethane resin (A). It is more preferable to use what has it because many pores having a relatively uniform size can be formed, and as a result, a porous body having both excellent moisture permeability and flexibility can be formed.
- the urethane resin (A) has 1 to 60% by mass of the polyoxyethylene structure with respect to the total mass of the urethane resin (A). It is preferable for obtaining a porous body excellent in.
- the urethane resin (A) When the urethane resin (A) is used alone or as a main component as the urethane resin constituting the porous body, the urethane resin (A) is 1 to 15% by mass with respect to the total amount of the urethane resin (A). Those having a polyoxyethylene structure are preferably used, and those having 2 to 10% by mass are more preferably used.
- the urethane resin (A) used in combination with the urethane resin (A) and the urethane resin (C) having no polyoxyethylene structure is used in combination with the urethane resin (A)
- the urethane resin (A) It is preferable to use those having a polyoxyethylene structure of 30 to 60% by mass relative to the total amount of A).
- the polyoxyethylene structure is preferably, for example, a structure represented by the following general formula (1), and n in the general formula (1) is more preferably an integer in the range of 1 to 100. An integer of ⁇ 50 is particularly preferred.
- the polyoxyethylene structure may be a structure in which a cyclic ether compound such as propylene oxide or tetrahydrofuran is reacted with a part of the structure represented by the general formula (1).
- the urethane resin (A) preferably has a weight average molecular weight of 5000 to 500,000.
- the urethane resin (A) when used alone or as a main component as the urethane resin constituting the porous body, the urethane resin (A) has a relatively high molecular weight having a weight average molecular weight of 50,000 to 500,000. It is preferable to use those having 100,000 to 300,000, in order to form a relatively uniform communication hole and to obtain a porous body having excellent moisture permeability and excellent strength.
- the urethane resin (A) and the urethane resin (C) not having a polyoxyethylene structure are used in combination as the urethane resin constituting the porous body
- the urethane resin (A) is 5000 to 20000.
- Those having a weight average molecular weight are preferably used, and those having a weight average molecular weight of 5000 to 15000 are formed with relatively uniform communication holes and excellent moisture permeability and excellent strength. It is more preferable when obtaining a porous body.
- urethane resin (A) having a polyoxyethylene structure those obtained by reacting a polyol (a1) and a polyisocyanate (a2) can be used.
- the polyol (a1) obtained by reacting the polyol (a1) with the polyisocyanate (a2) using a polyol (a1-1) having a polyoxyethylene structure can be used.
- the urethane resin (A) which has an isocyanate group in the molecular terminal obtained by making a polyol (a1) and polyisocyanate (a2) react polyoxyethylene alcohol (a3) ), A urethane resin having a polyoxyethylene structure at the molecular end obtained by reacting can be suitably used.
- the polyol (a1) which does not contain the polyol (a1-1) having the polyoxyethylene structure may be used.
- Examples of the polyol (a1-1) having a polyoxyethylene structure that can be used in the production of the urethane resin (A) include polyethylene glycol, block copolymers of polyoxyethylene and other polyoxyalkylenes, and random polymers. Etc. can be used.
- ethylene glycol, diethylene glycol, triethylene glycol or the like as an initiator, and addition polymerization of alkylene oxides such as ethylene oxide, propylene oxide, butylene oxide, styrene oxide, epichlorohydrin, tetrahydrofuran can be used.
- the initiator propylene glycol, trimethylene glycol, 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, glycerin, diglycerin, trimethylolethane, trimethylol
- an initiator such as propane, water, hexanetriol or the like
- one using ethylene oxide as the alkylene oxide can be used.
- the polyol (a1-1) having a polyoxyethylene structure has a weight average molecular weight of 500 to 5000 from the viewpoint of obtaining a porous body having relatively uniform communication holes and having excellent moisture permeability. It is preferable to use it.
- polyol (a1) other polyols other than the polyol (a1-1) having the polyoxyethylene structure can be used in combination.
- polyether polyols examples include polyether polyols, polyester polyols, and polycarbonate polyols.
- polyether polyols examples include polyether polyols, polyester polyols, and polycarbonate polyols.
- polyether polyol examples include those obtained by addition polymerization of alkylene oxide using one or more compounds having two or more active hydrogen atoms as an initiator. .
- the initiator examples include propylene glycol, trimethylene glycol, 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, glycerin, diglycerin, trimethylolethane, and trimethylol.
- Propane, water, hexanetriol and the like can be used.
- alkylene oxide for example, propylene oxide, butylene oxide, styrene oxide, epichlorohydrin, tetrahydrofuran and the like can be used.
- polypropylene glycol and polyoxytetramethylene glycol are preferable to use as the polyether polyol that can be used for the other polyols.
- polyester polyol examples include cyclic polyesters such as aliphatic polyester polyols, aromatic polyester polyols, and ⁇ -caprolactone obtained by esterifying low molecular weight polyols and polycarboxylic acids. Polyesters obtained by ring-opening polymerization reaction of ester compounds, copolymerized polyesters thereof, and the like can be used.
- the low molecular weight polyol for example, ethylene glycol, propylene glycol and the like can be used.
- polycarboxylic acid for example, succinic acid, adipic acid, sebacic acid, dodecanedicarboxylic acid, terephthalic acid, isophthalic acid, phthalic acid, and anhydrides or ester-forming derivatives thereof can be used.
- cyclic ester compound for example, ⁇ -caprolactone, ⁇ -butyrolactone and the like can be used.
- polycarbonate polyol examples include those obtained by reacting a carbonate with a polyol, and those obtained by reacting phosgene with bisphenol A or the like.
- carbonate ester methyl carbonate, dimethyl carbonate, ethyl carbonate, diethyl carbonate, cyclocarbonate, diphenyl carbonate, or the like can be used.
- polyol that can react with the carbonate ester examples include ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, dipropylene glycol, 1,4-butanediol, 1,3-Butanediol, 1,2-butanediol, 2,3-butanediol, 1,5-pentanediol, 1,5-hexanediol, 2,5-hexanediol, 1,6-hexanediol, 1,7-heptane Diol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, 3-methyl-1,5-pentanediol, 2- Ethyl-1,3-hexanediol, 2-methyl-1,3-
- the polyol (a1-1) having the polyoxyethylene structure is used in the range of 0.1 to 20% by mass relative to the total amount of the polyol (a1). It is preferable to form a uniform communication hole and obtain an excellent moisture-permeable porous body.
- acrylic polyol, polybutadiene polyol, hydrogenated polybutadiene polyol, partially saponified product of ethylene-vinyl acetate copolymer, and the like can be used as necessary. It can be used as long as it is not damaged.
- polyisocyanate (a2) capable of reacting with the polyol (a1) examples include phenylene diisocyanate, tolylene diisocyanate, 4,4′-diphenylmethane diisocyanate, naphthalene diisocyanate, polymethylene polyphenyl polyisocyanate, carbodiimidized diphenylmethane polyisocyanate.
- Aliphatic polycyclic isocyanate such as hexamethylene diisocyanate, lysine diisocyanate, cyclohexane diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, dimer acid diisocyanate, norbornene diisocyanate Structure-containing polyisocyanate Etc., it can be used in combination singly used or two or more.
- the use of the aromatic polyisocyanate is preferable for obtaining a urethane resin (A) that can be easily solidified by a wet method, and it is more preferable to use 4,4'-diphenylmethane diisocyanate.
- polyoxyethylene alcohol (a3) which can be used for manufacture of the urethane resin (A)
- polyethylene glycol, block copolymers of polyoxyethylene and other polyoxyalkylenes, random polymers, etc. are used. can do.
- what has sealed the hydroxyl group of one terminal can also be used conveniently.
- the polyoxyethylene alcohol (a3) preferably has a weight average molecular weight of 1000 to 5000.
- a chain extender can be used as needed.
- the urethane resin (A) is used alone or as a main component as the urethane resin forming the porous body, it is preferable to use a relatively high molecular weight urethane resin of 50,000 to 500,000. It is preferable to use a chain extender in combination.
- chain extender examples include ethylene glycol, 1,2-propanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, and 3-methyl-1,5-pentanediol.
- the urethane resin (A) includes, for example, a polyol (a1) containing the polyol (a1-1) having the polyoxyethylene structure and the polyisocyanate (a2) in the absence of a solvent or in the presence of an organic solvent (B) described later. ) And reacting with each other.
- the urethane resin (A) is a mixture of the polyol (a1), the polyisocyanate (a2), and the polyoxyethylene alcohol (a3), for example, in the absence of a solvent or in the presence of an organic solvent (B) described later. And a urethane having an isocyanate group at the molecular end by mixing and reacting the polyol (a1) and the polyisocyanate (a2) in the absence of a solvent or in the presence of an organic solvent (B) described later, for example.
- the resin (A ′) is manufactured, and then the urethane resin (A ′) and the polyoxyethylene alcohol (a3) are mixed, and the isocyanate group of the urethane resin (A ′) and the polyoxyethylene alcohol ( It can also be produced by a method of reacting a3) with a hydroxyl group.
- the chain extender when producing the urethane resin (A), the chain extender may be used and reacted when mixing the polyol (a1) and the polyisocyanate (a2), Further, after the polyol (a1) and the polyisocyanate (a2) are reacted to produce a urethane resin (A ′) having an isocyanate group at the molecular end, the urethane resin (A ′) and a chain extender are mixed. You may make it react.
- the equivalent ratio [isocyanate group / hydroxyl group] of the hydroxyl group of the polyol and the isocyanate group of the polyisocyanate (a2) is 0.8 to 1.
- the range of 1 is preferable, and the range of 0.9 to 1.0 is more preferable because the pore diameter in the porous body is relatively uniform, and both good moisture permeability and a soft texture can be achieved.
- the reaction is preferably carried out in the range of the equivalent ratio of 1.0 to 1.1 so that the molecular terminal of the urethane resin (A ′) is an isocyanate group. .
- the molecular terminal of the urethane resin (A ′) is an isocyanate group. It is preferable to carry out the reaction in an equivalence ratio of 1.0 to 1.1.
- the urethane resin (A) obtained by the method is preferably dissolved or dispersed in the organic solvent (B), and part of the urethane resin (A) is dissolved in the organic solvent (B). It is preferable that In addition, from the viewpoint of suppressing solidification of the urethane resin (A) in the organic solvent (B) and maintaining good storage stability over a long period of time, the urethane resin (A) contains the organic solvent (B), water and More preferably, it is in the state of a mixture dissolved or dispersed in the mixed solvent.
- reaction of the polyol (a1) and the polyisocyanate (a2) is performed in the presence of the organic solvent (B) to obtain a mixture of the urethane resin (A) and the organic solvent (B), It is preferable to mix water.
- the mixed solvent is preferably one containing water in the range of 1 to 30% by mass, preferably 1 to 10% by mass, based on the total amount of the mixed solvent. It is more preferable for maintaining stable storage stability.
- the urethane resin (C) is used in combination with the urethane resin (A) to form a porous body having a relatively uniform communication hole and having excellent moisture permeability. It is preferable in obtaining.
- urethane resin (C) that can be used in combination with the urethane resin (A)
- a urethane resin having no polyoxyethylene structure can be used.
- the urethane resin (C) having no polyoxyethylene group among the polyols (a1) exemplified as those usable for the production of the urethane resin (A), those having a polyoxyethylene structure polyol (a1) Those obtained by reacting other polyols other than -1), polyisocyanate (a2), and, if necessary, the chain extender can be used.
- polyol (a4) usable for the production of the urethane resin (C) among the polyols (a1) exemplified as those usable for the production of the urethane resin (A), a polyol having a polyoxyethylene structure ( Other than a1-1) can be used, and specifically, polyether polyol, polyester polyol and polycarbonate polyol having no polyoxyethylene structure can be used.
- the use of a polyether polyol and a polyester polyol that do not have a polyoxyethylene structure, or the use of a combination of the polyester polyol and the polycarbonate polyol makes it difficult to cause skinning and the like, and has excellent moisture permeability. It is preferable when obtaining a porous body.
- polyether polyols examples include propylene glycol, trimethylene glycol, 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, glycerin, A material obtained by addition polymerization of alkylene oxide other than ethylene oxide using trimethylolethane, trimethylolpropane or the like as an initiator can be used.
- alkylene oxide for example, propylene oxide, butylene oxide, styrene oxide, epichlorohydrin, tetrahydrofuran and the like can be used.
- polyether polyol it is particularly preferable to use polyoxytetramethylene glycol, polypropylene glycol or the like.
- polyester polyol and the polycarbonate polyol that can be used for the polyol (a4) the same polyester polyols and polycarbonate polyols that can be used for the polyol (a1) can be used.
- the urethane resin (C) can be produced, for example, by mixing and reacting the polyol (a4) and the polyisocyanate (a2) in the absence of a solvent or in the presence of an organic solvent (B) described later. .
- the equivalent ratio [isocyanate group / hydroxyl group] of the hydroxyl group of the polyol (a4) and the isocyanate group of the polyisocyanate (a2) is 0.8. It is preferably in the range of -1.1, and in the range of 0.9-1.0, the pore diameter in the porous body is relatively uniform, and it is possible to achieve both good moisture permeability and a soft texture. Therefore, it is more preferable.
- the urethane resin (C) obtained by the above method is preferably dissolved or dispersed in the organic solvent (B).
- the urethane resin (C) is a mixture of the organic solvent (B) and water dissolved or dispersed in a mixed solvent. More preferably, it is in a state.
- the reaction between the polyol (a4) and the polyisocyanate (a2) is performed in the presence of the organic solvent (B) to obtain a mixture of the urethane resin (C) and the organic solvent (B), It is preferable to mix water.
- the mixed solvent is preferably one containing water in the range of 1 to 30% by mass, preferably 1 to 10% by mass, based on the total amount of the mixed solvent. It is more preferable for maintaining stable storage stability.
- the mass ratio [(A) / (C)] is in the range of 0.1 / 100 to 10/100. It is preferable to obtain a porous body having a relatively uniform communication hole and having excellent moisture permeability without causing any problems.
- one or more selected from the group consisting of a ketone solvent and an ester solvent is used as an organic solvent used when producing a porous body by a wet method using the urethane resin (A) or the like.
- a ketone solvent and an ester solvent is used as an organic solvent used when producing a porous body by a wet method using the urethane resin (A) or the like.
- DMF dimethylformamide
- the wet method is used without using dimethylformamide. Therefore, it has been desired to develop a method for forming a porous body.
- urethane resin (A) having a polyoxyethylene structure is an essential component, and at least one selected from the group consisting of ketone solvents and ester solvents is selected in place of conventional dimethylformamide.
- the present invention has found that a porous body having very excellent moisture permeability can be formed even by a wet method.
- the surface of the porous body is skinned or relatively uniform even when the urethane resin (A) is used. In some cases, a continuous communication hole cannot be formed.
- ketone solvents that can be used for the organic solvent (B) include methyl ethyl ketone, methyl n-propyl ketone, acetone, and methyl isobutyl ketone.
- ester solvents that can be used in the organic solvent (B) include methyl formate, ethyl formate, propyl formate, methyl acetate, ethyl acetate, isopropyl acetate, isobutyl acetate, isobutyl acetate, and secondary butyl acetate. can do.
- the organic solvent (B) it is possible to use methyl ethyl ketone or ethyl acetate to suppress the occurrence of skinning and agglomerates and to form relatively uniform communication holes and to have excellent moisture permeability. It is preferable when obtaining a porous body.
- the organic solvent (B) preferably has a boiling point of 150 ° C. or lower and a water solubility at 25 ° C. of 50 g or lower, more preferably 1 to 50 g.
- the present invention does not exclude the use of other organic solvents in combination with the organic solvent (B) as the organic solvent, but the organic solvent (B) is the total amount of the organic solvent used in the present invention. It is preferably used in the range of 95 to 100% by mass, more preferably in the range of 98% to 100% by mass, and more preferably in the range of 99% to 100% by mass. It is particularly preferable to use only the organic solvent (B).
- organic solvents having higher water solubility such as tetrahydrofuran (THF) and dioxane
- those having lower water solubility such as benzene, toluene, n-hexane, and 1,2-dichloroethane.
- a mixed solvent with an organic solvent can be used.
- the mixed solvent has a boiling point of 150 ° C. or lower and a water solubility at 25 ° C. of 50 g or lower, more preferably 1 to 50 g. Is preferred.
- organic solvent (B) may be used in combination with the organic solvent (B).
- organic solvent tetrahydrofuran, a dioxane, etc. can be used, for example.
- the organic solvent (B) is preferably used in a range of 50 to 80% by mass, based on the total amount of the urethane resin (A) and the urethane resin (C) used in the present invention, and 60 to 80% by mass. % Is more preferable.
- the urethane resin composition used in the present invention can be produced, for example, by mixing the urethane resin (A) produced in the absence of a solvent and the organic solvent (B). Moreover, the urethane resin composition which consists of a mixture of a urethane resin (A) and an organic solvent (B) by making the said polyol (a1), the said polyisocyanate (a2), etc. react in presence of an organic solvent (B). You may manufacture things.
- the said urethane resin (C) when using together the said urethane resin (C), it can manufacture by mixing the urethane resin (A) and urethane resin (C) which were manufactured separately, and the organic solvent (B).
- the urethane resin (C) is produced in the presence of the organic solvent (B), a mixture of the urethane resin (A) and the organic solvent (B), the urethane resin (C) and the organic solvent. It can also be produced by mixing a mixture with (B).
- the urethane resin composition preferably contains water.
- the water is preferably in the range of 1 to 30% by mass and preferably in the range of 1 to 10% by mass with respect to the total amount of the organic solvent (B) and water contained in the urethane resin composition. It is more preferable.
- the urethane resin composition may contain other additives as necessary in addition to the above.
- the additive may be colored with, for example, an organic pigment or an inorganic pigment, and further contains a brominated flame retardant, a chlorinated flame retardant, a plasticizer, a softening agent, a stabilizer, a wax, an extinguishing agent, if necessary.
- the additive to be used can be used in the range which does not inhibit the effect of this invention.
- the urethane resin composition is applied or impregnated on the surface of a base material, and then water or A porous body is formed by bringing water vapor into contact and solidifying the urethane resin (A) or urethane resin (C) contained in the urethane resin composition by a wet method. And a method of producing by washing with hot water and drying.
- a non-woven fabric, a woven fabric, a knitted base material, a resin film, or the like can be used as the base material on which the urethane resin composition is applied.
- a material constituting the base material for example, polyester fiber, nylon fiber, acrylic fiber, polyurethane fiber, acetate fiber, rayon fiber, polylactic acid fiber, cotton, hemp, silk, wool, blended fiber thereof or the like is used. can do.
- the surface of the base material may be subjected to antistatic processing, mold release processing, water repellent processing, water absorption processing, antibacterial deodorization processing, antibacterial processing, ultraviolet blocking processing and the like as necessary.
- Examples of the method of applying or impregnating the urethane resin composition on the surface of the substrate include a gravure coater method, a knife coater method, a pipe coater method, and a comma coater method. At that time, from the viewpoint of adjusting the viscosity of the urethane resin composition and improving the coating workability, an organic solvent (B), water, or the like may be used as necessary.
- the urethane resin composition 10 to 100 parts by mass of the organic solvent (B) is supplied to 100 parts by mass of the urethane resin composition immediately before being applied or impregnated on the surface of the base material, or 10 It is preferable to use water supplied in the range of 100 to 100 parts by mass in order to efficiently form a relatively large number of pores, and it is more preferable to use water in the range of 30 to 80 parts by mass. .
- the film thickness of the urethane resin composition applied or impregnated by the above method is preferably about 0.5 mm to 5.0 mm, and more preferably about 0.5 mm to 3 mm.
- a substrate provided with a coating layer or an impregnation layer made of the urethane resin composition is immersed in a water bath.
- a method and a method of spraying water vapor on the coated surface using a spray or the like are examples thereof.
- the immersion is preferably performed for about 10 to 60 minutes in a warm water bath at about 25 to 60 ° C.
- spray warm water adjusted to about 25 to 60 ° C. for about 10 to 60 minutes.
- the surface of the porous body formed by the above method is preferably washed with normal temperature water or hot water of about 30 to 60 ° C., if necessary, and then dried.
- the drying is preferably performed for about 10 to 30 minutes using a dryer or the like adjusted to about 80 to 120 ° C.
- the porous body obtained by the above method has a porous structure composed of uniform and fine communication holes.
- the size of the hole can be adjusted as appropriate according to the application, but preferably has a diameter of 1 ⁇ m to 10 ⁇ m from the viewpoint of achieving both excellent moisture permeability, soft texture, strength, and the like.
- the porous body obtained by the present invention is a continuous hole in which a plurality of such holes are continuous, it has a moisture permeability superior to each stage as compared with a porous body obtained by a conventional wet method. It has an excellent moisture permeability comparable to the porous body obtained by the dry method.
- the thickness of the porous body can be appropriately adjusted according to the use etc. by adjusting the composition of the urethane resin (A) or the urethane resin (C), but it has both excellent moisture permeability and flexible texture. From this viewpoint, a porous film or a porous film having a thickness in the range of 10 ⁇ m to 500 ⁇ m is preferable.
- the moisture permeability of the porous body obtained by the above method is preferably 4000 to 20000 g / m when measured by a moisture permeability test method in accordance with the Japanese Industrial Standard JIS L 1099-1993 A-1 method (calcium chloride method).
- the range is 2 ⁇ 24 hrs, more preferably 5000 to 20000 g / m 2 ⁇ 24 hrs.
- the porous body obtained by the production method of the present invention has excellent moisture permeability and breathability, and has a flexible texture.
- leather-like sheets such as synthetic leather and artificial leather used for medical treatment, medical hygiene materials such as surgical clothes and bed sheets, sheets for building materials such as wind and waterproof sheets and anti-condensation sheets, desiccants, dehumidifiers and fragrances
- the intermediate layer constituting the packaging material, agricultural sheet, various separators, packing and the like can be used for various applications such as a skin layer.
- Example 1 (Preparation of urethane resin composition (I))
- a reactor having a stirrer and a thermometer 103 parts by mass of polyoxytetramethylene glycol (weight molecular weight 1800), 70 parts by mass of polybutylene adipate (weight molecular weight 2000), 3 parts by mass of polyethylene glycol (weight average molecular weight 1540) and 4,
- 103 parts by weight of 4′-diphenylmethane diisocyanate in 128 parts by weight of methyl ethyl ketone with stirring at 60 ° C. for 2 hours, a mixture of polyurethane (A′-1) having an isocyanate group at the molecular end and methyl ethyl ketone is obtained. It was.
- a urethane resin composition (I) containing a urethane resin (A-1) having a weight-average molecular weight of 120,000 and having a polyoxyethylene structure, methyl ethyl ketone and water (non-volatile content 30% by mass, viscosity 15000 mPa ⁇ s) was obtained. Even when the urethane resin composition (I) was allowed to stand in an environment of 25 ° C. for 2 months, the urethane resin composition (I) was hardly thickened and had good storage stability.
- the urethane resin composition (I) was applied to the surface of a nonwoven fabric made of polyester fiber using a comma coater so that the applied film thickness was about 1.2 mm, and then the applied material was adjusted to 25 ° C. in water.
- the urethane resin (A-1) contained in the urethane resin composition (I) was wet coagulated for 10 minutes.
- the surface of the coated product is washed by immersing it in warm water adjusted to 50 ° C. for 30 minutes, and then dried for 20 minutes using a hot air dryer adjusted to 100 ° C., thereby forming uniform and fine communication holes.
- Example 2 (Preparation of urethane resin composition (II))
- a reactor having a stirrer and a thermometer 103 parts by mass of polyoxytetramethylene glycol (weight molecular weight 1800), 70 parts by mass of polybutylene adipate (weight molecular weight 2000), 3 parts by mass of polyethylene glycol (weight average molecular weight 1540) and 4,
- 103 parts by weight of 4′-diphenylmethane diisocyanate in 128 parts by weight of acetone at 60 ° C. for 2 hours with stirring, a mixture of polyurethane (A′-2) having an isocyanate group at the molecular terminal and acetone is obtained. It was.
- urethane resin composition (II) containing a urethane resin (A-2) having a weight-average molecular weight of 120,000 and having a polyoxyethylene structure, acetone and water (nonvolatile content: 30% by mass, viscosity: 15000 mPa ⁇ s) was obtained.
- the porous body (II ⁇ ) was prepared in the same manner as in Example 1 (Preparation of porous body and leather-like sheet). 1) and a leather-like sheet (II-2) were produced.
- Example 3 (Preparation of urethane resin composition (III))
- a reactor having a stirrer and a thermometer 103 parts by mass of polyoxytetramethylene glycol (weight molecular weight 1800), 70 parts by mass of polybutylene adipate (weight molecular weight 2000), polyethylene alcohol having one hydroxyl group at one end (M- 2000, manufactured by NOF Corporation, weight average molecular weight 2000) 3 parts by mass and 103 parts by mass of 4,4′-diphenylmethane diisocyanate were reacted in 128 parts by mass of methyl ethyl ketone at 60 ° C. for 2 hours with stirring to obtain molecular terminals.
- a mixture of polyurethane (A′-3) having an isocyanate group and methyl ethyl ketone was obtained.
- Example 4 (Preparation of urethane resin composition (IV))
- a reactor having a stirrer and a thermometer 103 parts by mass of polyoxytetramethylene glycol (weight molecular weight 1800), 70 parts by mass of polybutylene adipate (weight molecular weight 2000), polyethylene alcohol having one hydroxyl group at one end (M- 2000, manufactured by NOF Corporation, weight average molecular weight 2000) 3 parts by mass and 103 parts by mass of 4,4′-diphenylmethane diisocyanate were reacted in acetone at 128 parts by mass at 60 ° C. for 2 hours with stirring.
- a mixture of polyurethane (A′-4) having an isocyanate group and acetone was obtained.
- urethane resin composition (IV) nonvolatile content: 30% by mass, viscosity: 15000 mPa ⁇ s
- a urethane resin composition (A-4) having a polyoxyethylene structure having a weight average molecular weight of 120,000, acetone and water was obtained.
- Example 5 (Preparation of urethane resin composition (V))
- a reaction apparatus having a stirrer and a thermometer
- 214 parts by mass of polypropylene glycol (weight molecular weight 2000) and 39 parts by mass of 4,4′-diphenylmethane diisocyanate are reacted in 330 parts by mass of methyl ethyl ketone at 80 ° C. for 2 hours with stirring.
- A′-5 having an isocyanate group at the molecular end and methyl ethyl ketone was obtained.
- 126 parts by mass of methyl ethyl ketone and 21 parts by mass of ethylene glycol as a chain extender were added to the mixture with stirring, and reacted at 60 ° C. for 4 hours.
- 416 parts by mass of methyl ethyl ketone are sequentially supplied in accordance with the increase in the viscosity of the mixture, and the reaction is continued while adjusting the viscosity of the mixture.
- a mixture of urethane resin (C-1) having a weight average molecular weight of 120,000, methyl ethyl ketone, and water (non-volatile content: 30% by mass) having no polyoxyethylene structure was obtained.
- Example 6 (Preparation of urethane resin composition (VI))
- a reaction apparatus having a stirrer and a thermometer
- 214 parts by mass of polypropylene glycol (weight molecular weight 2000) and 39 parts by mass of 4,4′-diphenylmethane diisocyanate are reacted in 330 parts by mass of acetone at 80 ° C. for 2 hours with stirring.
- A′-6 polyurethane having an isocyanate group at the molecular terminal and acetone was obtained.
- a urethane resin composition (VI) containing a urethane resin (A-6) having a weight average molecular weight of 7500, a urethane resin (C-2) having a weight average molecular weight of 120,000, methyl ethyl ketone, and water (nonvolatile content of about 30 Mass%, a viscosity of 15000 mPa ⁇ s, and a mass ratio [A-6 / C-2] 1/26) of the urethane resin (A-6) and the urethane resin (C-2).
- the porous body (VI--) was prepared in the same manner as in Example 1 (Preparation of porous body and leather-like sheet). 1) and a leather-like sheet (VI-2) were prepared.
- Example 7 (Preparation of urethane resin composition (VII))
- a reactor having a stirrer and a thermometer 103 parts by mass of polyoxytetramethylene glycol (weight molecular weight 1800), 70 parts by mass of polybutylene adipate (weight molecular weight 2000), 3 parts by mass of polyethylene glycol (weight average molecular weight 1540) and 4,
- 103 parts by weight of 4′-diphenylmethane diisocyanate in 128 parts by weight of methyl ethyl ketone with stirring at 60 ° C. for 2 hours, a mixture of polyurethane (A′-7) having an isocyanate group at the molecular end and methyl ethyl ketone is obtained. It was.
- urethane resin composition (VII) containing a resin (A-7) and methyl ethyl ketone (non-volatile content: 30% by mass, viscosity: 15000 mPa ⁇ s) was obtained.
- the urethane resin composition (VII) was thickened when left in an environment at 25 ° C. for 2 months, and was slightly inferior in terms of storage stability over a long period of time.
- urethane resin composition (VII) (Preparation of porous body and leather-like sheet) Using a comma coater, apply the urethane resin composition (VII) immediately after preparation to the surface of the nonwoven fabric made of polyester fiber so that the applied film thickness is about 1.2 mm, and then adjust the applied material to 25 ° C.
- the urethane resin (A-7) contained in the urethane resin composition (VII) was wet-coagulated by dipping in the water for 10 minutes.
- the surface of the coated product is washed by immersing it in warm water adjusted to 50 ° C. for 30 minutes, and then dried for 20 minutes using a hot air dryer adjusted to 100 ° C., thereby forming uniform and fine communication holes.
- the urethane resin composition (VIII) was applied to the surface of the nonwoven fabric made of polyester fiber using a comma coater so that the coating film thickness was about 1.2 mm, and then the coating material was dried at 70 ° C.
- the leather-like sheet (VIII-) in which the porous body (VIII-1) is laminated on the surface of the nonwoven fabric is dried by a drying method in which the porous body (VIII-1) is dried for 20 minutes using a dryer and then dried for 20 minutes using a dryer adjusted to 120 ° C. 2) was obtained.
- 126 parts by mass of dimethylformamide ⁇ and 21 parts by mass of ethylene glycol ⁇ ⁇ ⁇ as a chain extender were added to the mixture with stirring, and reacted at 60 ° C for 4 hours.
- 446 parts by mass of dimethylformamide is sequentially supplied in accordance with the increase in the viscosity of the mixture, and the reaction is continued while adjusting the viscosity of the mixture, thereby having a polyoxyethylene structure having a weight average molecular weight of 120,000.
- a urethane resin composition (IX) containing a urethane resin (A-9) and dimethylformamide (nonvolatile content: 30% by mass, viscosity: 15000 mPa ⁇ s) was obtained.
- a urethane resin composition (X) containing a urethane resin (A-10) having a weight average molecular weight of 7500, a urethane resin (C-3) having a weight average molecular weight of 120,000 and dimethylformamide (non-volatile content of about 30 mass) %, A viscosity of 15000 mPa ⁇ s, and a mass ratio [A-9 / C-3] 1/26) of the urethane resin (A-10) and the urethane resin (C-3).
- FIG. 1 is a photograph of a cross section of the porous body constituting the leather-like sheet obtained in Example 5 taken at a magnification of 500 using a scanning electron microscope (SEM).
- SEM scanning electron microscope
- FIG. 2 is a photograph of the surface of the porous body constituting the leather-like sheet obtained in Example 5 taken at a magnification of 500 using a scanning electron microscope (SEM).
- Example 5 it can be clearly determined that the porous body obtained in Example 5 has a relatively uniform and fine porous structure (communication hole) formed therethrough.
- FIG. 3 is a photograph of a cross section of the porous body constituting the leather-like sheet obtained in Comparative Example 2 taken at a magnification of 500 using a scanning electron microscope (SEM).
- FIG. 4 is a photograph of the surface of the porous body constituting the leather-like sheet obtained in Comparative Example 2 taken at a magnification of 500 using a scanning electron microscope (SEM).
- the porous body obtained in Comparative Example 2 has a vertically long void (hole), but does not have a fine porous structure (communication hole) penetrating them. Can be clearly identified.
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- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
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- Dispersion Chemistry (AREA)
- Textile Engineering (AREA)
- Emergency Medicine (AREA)
- Synthetic Leather, Interior Materials Or Flexible Sheet Materials (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
- Polyurethanes Or Polyureas (AREA)
- Laminated Bodies (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
Abstract
Description
(ウレタン樹脂組成物(I)の調製)
攪拌機、温度計を有する反応装置に、ポリオキシテトラメチレングリコール(重量分子量1800)103質量部、ポリブチレンアジペート(重量分子量2000)70質量部、ポリエチレングリコール(重量平均分子量1540)3質量部及び4,4’-ジフェニルメタンジイソシアネート103質量部を、メチルエチルケトン128質量部中で、攪拌下60℃で2時間反応させることによって、分子末端にイソシアネート基を有するポリウレタン(A’-1)とメチルエチルケトンとの混合物を得た。
ポリエステル繊維からなる不織布の表面に、前記ウレタン樹脂組成物(I)をコンマコーター用いて、塗布膜厚が約1.2mmとなるように塗布し、次いで、前記塗布物を25℃に調整した水中に10分間浸漬させ、前記ウレタン樹脂組成物(I)中に含まれるウレタン樹脂(A-1)を湿式凝固させた。
(ウレタン樹脂組成物(II)の調製)
攪拌機、温度計を有する反応装置に、ポリオキシテトラメチレングリコール(重量分子量1800)103質量部、ポリブチレンアジペート(重量分子量2000)70質量部、ポリエチレングリコール(重量平均分子量1540)3質量部及び4,4’-ジフェニルメタンジイソシアネート103質量部を、アセトン128質量部中で、攪拌下60℃で2時間反応させることによって、分子末端にイソシアネート基を有するポリウレタン(A’-2)とアセトンとの混合物を得た。
ウレタン樹脂組成物(I)の代わりにウレタン樹脂組成物(II)を使用すること以外は、前記実施例1の(多孔体及び皮革様シートの作製)と同様の方法によって、多孔体(II-1)及び皮革様シート(II-2)を作製した。
(ウレタン樹脂組成物(III)の調製)
攪拌機、温度計を有する反応装置に、ポリオキシテトラメチレングリコール(重量分子量1800)103質量部、ポリブチレンアジペート(重量分子量2000)70質量部、片末端に1個の水酸基を有するポリエチレンアルコール(M-2000、日本油脂株式会社製、重量平均分子量2000)3質量部及び4,4’-ジフェニルメタンジイソシアネート103質量部を、メチルエチルケトン128質量部中で、攪拌下60℃で2時間反応させることによって、分子末端にイソシアネート基を有するポリウレタン(A’-3)とメチルエチルケトンとの混合物を得た。
ウレタン樹脂組成物(I)の代わりにウレタン樹脂組成物(III)を使用すること以外は、前記実施例1の(多孔体及び皮革様シートの作製)と同様の方法によって、多孔体(III-1)及び皮革様シート(III-2)を作製した。
(ウレタン樹脂組成物(IV)の調製)
攪拌機、温度計を有する反応装置に、ポリオキシテトラメチレングリコール(重量分子量1800)103質量部、ポリブチレンアジペート(重量分子量2000)70質量部、片末端に1個の水酸基を有するポリエチレンアルコール(M-2000、日本油脂株式会社製、重量平均分子量2000)3質量部及び4,4’-ジフェニルメタンジイソシアネート103質量部を、アセトン128質量部中で、攪拌下60℃で2時間反応させることによって、分子末端にイソシアネート基を有するポリウレタン(A’-4)とアセトンとの混合物を得た。
ウレタン樹脂組成物(I)の代わりにウレタン樹脂組成物(IV)を使用すること以外は、前記実施例1の(多孔体及び皮革様シートの作製)と同様の方法によって、多孔体(IV-1)及び皮革様シート(IV-2)を作製した。
(ウレタン樹脂組成物(V)の調製)
攪拌機、温度計を有する反応装置に、ポリプロピレングリコール(重量分子量2000)214質量部及び4,4’-ジフェニルメタンジイソシアネート39質量部を、メチルエチルケトン330質量部中で、攪拌下80℃で2時間反応させることによって、分子末端にイソシアネート基を有するポリウレタン(A’-5)とメチルエチルケトンとの混合物を得た。
ウレタン樹脂組成物(I)の代わりにウレタン樹脂組成物(V)を使用すること以外は、前記実施例1の(多孔体及び皮革様シートの作製)と同様の方法によって、多孔体(V-1)及び皮革様シート(V-2)を作製した。
(ウレタン樹脂組成物(VI)の調製)
攪拌機、温度計を有する反応装置に、ポリプロピレングリコール(重量分子量2000)214質量部及び4,4’-ジフェニルメタンジイソシアネート39質量部を、アセトン330質量部中で、攪拌下80℃で2時間反応させることによって、分子末端にイソシアネート基を有するポリウレタン(A’-6)とアセトンとの混合物を得た。
(ウレタン樹脂組成物(VII)の調製)
攪拌機、温度計を有する反応装置に、ポリオキシテトラメチレングリコール(重量分子量1800)103質量部、ポリブチレンアジペート(重量分子量2000)70質量部、ポリエチレングリコール(重量平均分子量1540)3質量部及び4,4’-ジフェニルメタンジイソシアネート103質量部を、メチルエチルケトン128質量部中で、攪拌下60℃で2時間反応させることによって、分子末端にイソシアネート基を有するポリウレタン(A’-7)とメチルエチルケトンとの混合物を得た。
ポリエステル繊維からなる不織布の表面に、調製直後のウレタン樹脂組成物(VII)をコンマコーター用いて、塗布膜厚が約1.2mmとなるように塗布し、次いで、前記塗布物を25℃に調整した水中に10分間浸漬させ、前記ウレタン樹脂組成物(VII)中に含まれるウレタン樹脂(A-7)を湿式凝固させた。
(ウレタン樹脂組成物(VIII)の調製)
攪拌機、温度計を有する反応装置に、ポリオキシテトラメチレングリコール(重量分子量1800)103質量部、ポリブチレンアジペート(重量分子量2000)70質量部、ポリエチレングリコール3質量部及び4,4’-ジフェニルメタンジイソシアネート 103質量部を、メチルエチルケトン128質量部中で、攪拌下60℃で2時間反応させることによって、分子末端にイソシアネート基を有するポリウレタン(A’-8)とメチルエチルケトンとの混合物を得た。
ポリエステル繊維からなる不織布の表面に、前記ウレタン樹脂組成物(VIII)をコンマコーター用いて、塗布膜厚が約1.2mmとなるように塗布し、次いで、前記塗布物を70℃に調整した乾燥機を用いて20分間乾燥させ、次に120℃に調整した乾燥機を用いて20分間乾燥させる乾式法によって、多孔体(VIII-1)が前記不織布表面に積層された皮革様シート(VIII-2)を得た。
(ウレタン樹脂組成物(IX)の調製)
攪拌機、温度計を有する反応装置に、ポリオキシテトラメチレングリコール(重量分子量1800)103質量部、ポリブチレンアジペート(重量分子量2000)70質量部、ポリエチレングリコール3質量部及び4,4’-ジフェニルメタンジイソシアネート103質量部を、ジメチルホルムアミド128質量部中で、攪拌下60℃で2時間反応させることによって、分子末端にイソシアネート基を有するポリウレタン(A’-9)とメチルエチルケトンとの混合物を得た。
ウレタン樹脂組成物(I)の代わりにウレタン樹脂組成物(IX)を使用すること以外は、前記実施例1の(多孔体及び皮革様シートの作製)と同様の方法によって、多孔体(IX-1)及び皮革様シート(IX-2)を作製した。
(ウレタン樹脂組成物(X)の調製)
攪拌機、温度計を有する反応装置に、ポリプロピレングリコール(重量分子量2000)214質量部及び4,4’-ジフェニルメタンジイソシアネート39質量部を、ジメチルホルムアミド330質量部中で、攪拌下60℃で2時間反応させることによって、分子末端にイソシアネート基を有するポリウレタン(A’-10)とジメチルホルムアミドとの混合物を得た。
ウレタン樹脂組成物(I)の代わりにウレタン樹脂組成物(X)を使用すること以外は、前記実施例1の(多孔体及び皮革様シートの作製)と同様の方法によって、多孔体(X-1)及び皮革様シート(X-2)を作製した。
前記ウレタン樹脂の数平均分子量は、ポリスチレン換算によるゲル・パーミエイション・クロマトグラフ(GPC;カラム;KD-806M(昭和電工株式会社製)、溶離液;ジメチルホルムアミド)により測定した。測定には、前記ウレタン樹脂のジメチルホルムアミド溶液(不揮発分;0.4質量%)を調製し使用した。
前記ウレタン樹脂組成物の粘度は、前記ウレタン樹脂組成物100質量部をガラス瓶に入れ、これを水温25℃に温度設定した恒温水槽に浸すことによって25℃に調整し、次いで、デジタル粘度計TV-10(TOKISANGYO製)を用い、測定温度:25℃、回転数:12rpm、回転棒:ロットNo.4の条件で測定した。
前記方法で得られた皮革様シートの透湿度を、日本工業規格 JIS L 1099-1993 A-1法(塩化カルシウム法)に準拠する透湿度試験方法によって測定し、該測定値を24時間当りの透湿量に換算した。
前記方法で得られた皮革様シートを構成する多孔体表面を走査型電子顕微鏡(SEM)を用いて観察し、多孔体表面の凝集物の付着の有無を確認した。
ジメチルホルムアミドを使用することなく湿式法により多孔体を形成できたものを「○」、ジメチルホルムアミドを使用することなく多孔体を形成できたものの有機溶剤の回収等が困難な乾式法で行ったものを「△」、ジメチルホルムアミドを使用することによって多孔体を形成したもの、または、多孔体を形成できなかったものを「×」と評価した。
Claims (19)
- ポリオキシエチレン構造を有するウレタン樹脂(A)と、ケトン系溶剤及びエステル系溶剤からなる群より選ばれる1種以上の有機溶剤(B)とを含有するウレタン樹脂組成物を、基材表面に塗布または含浸し、次いで、該塗布面または含浸面に水または水蒸気を接触させることによって前記ウレタン樹脂(A)を湿式凝固させることを特徴とする多孔体の製造方法。
- 前記ウレタン樹脂(A)が、50000~500000の重量平均分子量を有するものである、請求項1に記載の多孔体の製造方法。
- 前記ウレタン樹脂(A)が分子末端にポリオキシエチレン構造を有するものである、請求項1に記載の多孔体の製造方法。
- 前記ウレタン樹脂(A)が、ポリエーテルポリオール及びポリエステルポリオールからなる群より選ばれる1種以上を含有するポリオール(a1)とポリイソシアネート(a2)とを反応させて得られる分子末端にイソシアネート基を有するウレタン樹脂(A’)、及び、ポリオキシエチレンアルコール(a3)を反応させて得られる、分子末端にポリオキシエチレン構造を有するウレタン樹脂である、請求項1に記載の多孔体の製造方法。
- 前記有機溶剤(B)の含有量が、前記ウレタン樹脂組成物中に含まれる有機溶剤の全量に対して95~100質量%である、請求項1に記載の多孔体の製造方法。
- 前記有機溶剤(B)が、メチルエチルケトン、アセトン及び酢酸エチルからなる群より選ばれる1種以上である、請求項1または5に記載の多孔体の製造方法。
- 前記ウレタン樹脂組成物が、前記ウレタン樹脂(A)の全量に対して前記有機溶剤(B)を50~80質量%含有する、請求項1に記載の多孔体の製造方法。
- 前記ウレタン樹脂組成物が、更に水を含有するものであって、前記水が前記有機溶剤(B)及び前記水の合計量に対して1~30質量%含まれるものである、請求項1に記載の多孔体の製造方法。
- ポリオキシエチレン構造を有するウレタン樹脂(A)と、ケトン系溶剤及びエステル系溶剤からなる群より選ばれる1種以上の有機溶剤(B)と、ポリオキシエチレン構造を有さないウレタン樹脂(C)とを含有するウレタン樹脂組成物を、基材表面に塗布または含浸し、次いで、該塗布面または含浸面に水または水蒸気を接触させることによって前記ウレタン樹脂(A)及び前記ウレタン樹脂(C)を湿式凝固させることを特徴とする多孔体の製造方法。
- 前記ウレタン樹脂(A)が5000~20000の重量平均分子量を有するものであり、かつ、前記ウレタン樹脂(C)が50000~500000の重量平均分子量を有するものである、請求項9に記載の多孔体の製造方法。
- 前記ウレタン樹脂(A)と前記ウレタン樹脂(C)との質量割合[(A)/(C)]が0.1/100~10/100の範囲である、請求項9に記載の多孔体の製造方法。
- 前記ウレタン樹脂(A)が、分子末端にポリオキシエチレン構造を有するものである、請求項9に記載の多孔体の製造方法。
- 前記ウレタン樹脂(A)が、ポリエーテルポリオール及びポリエステルポリオールからなる群より選ばれる1種以上を含むポリオール(a1)とポリイソシアネート(a2)とを反応させて得られる分子末端にイソシアネート基を有するウレタン樹脂(A’)、及び、ポリオキシエチレンアルコール(a3)を反応させて得られる、分子末端にポリオキシエチレン構造を有するウレタン樹脂である、請求項9に記載の多孔体の製造方法。
- 前記有機溶剤(B)の含有量が、前記ウレタン樹脂組成物中に含まれる有機溶剤の全量に対して95~100質量%である、請求項9に記載の多孔体の製造方法。
- 前記有機溶剤(B)が、メチルエチルケトン及び酢酸エチルからなる群より選ばれる1種以上である、請求項9または14に記載の多孔体の製造方法。
- 前記ウレタン樹脂組成物が、前記ウレタン樹脂(A)及び前記ウレタン樹脂(C)の全量に対して前記有機溶剤(B)を50~80質量%含有する、請求項9に記載の多孔体の製造方法。
- 前記ウレタン樹脂組成物が、更に水を含有するものであって、前記水が前記有機溶剤(B)と前記水との合計量に対して1~30質量%含まれるものである、請求項9に記載の多孔体の製造方法。
- 基材表面に、請求項1~17のいずれかの製造方法によって得られた多孔体からなる多孔層が積層された積層体。
- 基材表面に、請求項1~17のいずれかの製造方法によって得られた多孔体からなる多孔層が積層された皮革様シート。
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