EP0603410B1 - Moisture-permeable waterproof cloth and production thereof - Google Patents
Moisture-permeable waterproof cloth and production thereof Download PDFInfo
- Publication number
- EP0603410B1 EP0603410B1 EP93913547A EP93913547A EP0603410B1 EP 0603410 B1 EP0603410 B1 EP 0603410B1 EP 93913547 A EP93913547 A EP 93913547A EP 93913547 A EP93913547 A EP 93913547A EP 0603410 B1 EP0603410 B1 EP 0603410B1
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- European Patent Office
- Prior art keywords
- resin
- moisture
- temperature
- fabric
- woven fabric
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Classifications
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M23/00—Treatment of fibres, threads, yarns, fabrics or fibrous goods made from such materials, characterised by the process
- D06M23/10—Processes in which the treating agent is dissolved or dispersed in organic solvents; Processes for the recovery of organic solvents thereof
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/564—Polyureas, polyurethanes or other polymers having ureide or urethane links; Precondensation products forming them
- D06M15/568—Reaction products of isocyanates with polyethers
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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
Definitions
- the present invention relates to a moisture-permeable waterproof fabric and a process for producing it. More particularly, the present invention is concerned with a comfortable moisture-permeable waterproof fabric, which can control the moisture permeability and heat retaining property so as to correspond with required bodily sensations, regarding warmth and coldness, and a process for producing it. In particular, it relates to such fabrics having on at least one surface a polyurethane resin fiber.
- FR-A-2369815 describes a process for making polyurethane foam backed carpets for the automobile industry.
- the polyurethane may be produced from an isocyanate, a polyether (obtainable by polymerization of an epoxide and having a molecular weight of 400 to 10,000) and a chain extender.
- DE-A-2431846 discloses a process for laminating a fabric with a polyurethane coating by means of an adhesive in which respective solutions of the polyurethane and adhesive are applied, each solution containing the same solvent in order to improve the process.
- the polyurethane may be produced from an isocyanate, a polyether (obtainable by polymerization of an epoxide and having a molecular weight of 600 to 4,000) and a chain extender.
- An object of the present invention is to provide a moisture-permeable waterproof woven fabric having real comfortability, characterised by having a high heat retaining property when the service temperature is low while enjoying a high water-vapour permeability to provide coolness when the service temperature is high, and a process for producing it.
- the present invention provides a moisture-permeable waterproof woven, knitted or non-woven fabric comprising a woven, knitted or non-woven fabric substrate and provided on at least one surface of the fabric substrate, a resin film comprising a polyurethane resin produced by reacting an isocyanate component with a polyol component and a chain extender and having a glass transition temperature in the range of from -20 to 20°C and an ethylene oxide unit content of at least 7.0 mol/kg.
- the fabric useful for the present invention may comprise a chemical fiber, such as a polyester, polyamide, acrylic or rayon fiber, a natural fiber, such as cotton or wool, or a mixture thereof. They may be in the form of any of a woven fabric, a knitted fabric and a nonwoven fabric.
- a component having a rigid structure serving to suppress the molecular motion is used for constituting the polyurethane resin to bring the glass transition temperature of the polyurethane resin to the range of from -20 to 20°C, thereby rendering the moisture permeability of the woven fabric highly dependent upon the temperature.
- isocyanates commonly used in polyurethane may be used as the isocyanate component.
- Preferred examples thereof include 4,4'-diphenylmethane diisocyanate (MDI), hydrogenated MDI, isophorone diisocyanate, 1,3-xylene diisocyanate, 2,4-tolylene diisocyanate and m-phenylene diisocyanate. They may be used alone or in the form of a mixture of two or more of them. MDI and hydrogenated MDI are still preferred from the viewpoint of rigidity of the molecular structure.
- MDI 4,4'-diphenylmethane diisocyanate
- hydrogenated MDI isophorone diisocyanate
- 1,3-xylene diisocyanate 1,3-xylene diisocyanate
- 2,4-tolylene diisocyanate 2,4-tolylene diisocyanate
- m-phenylene diisocyanate m-phenylene diisocyanate
- the chain extender may also be one known in the art.
- Preferred examples thereof include ethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol, ethylenediamine, trimethylenediamine, isophoronediamine and water. They may be used alone or in the form of a mixture of two or more of them. Ethylene glycol, propylene glycol and water are particularly preferred from the viewpoint of rigidity of the molecular structure.
- the polyol component may be one known in the art, and examples thereof include high-molecular weight diols, such as polyethylene glycol which is a product of addition homopolymerization of ethylene oxide, an ethylene oxide adduct of tetrahydrofuran which is a copolymer of ethylene oxide with another compound, an ethylene oxide adduct of bisphenol A, a condensate of adipic acid with ethylene oxide and an ethylene oxide adduct of polybutylene glycol adipate diol or polypropylene glycol adipate diol, and high-molecular weight diols not containing ethylene oxide, such as polytetramethylene glycol, polypropylene ether glycol, poly- ⁇ -caprolactone glycol, polybutyrolactone glycol, polypropylene glycol adipate diol and polybutylene glycol adipate diol. They may be used alone or in the form of a mixture of two or more
- the polyol preferably has a molecular weight in the range of from 500 to 3,000.
- the molecular weight is less than 500, the elastomeric performance of the resultant polyurethane resin is unsatisfactory, which results in poor durability during use.
- the molecular weight is more than 3,000, conditions for synthesis are limited, which leads to a problem that when a film is formed from the resultant polyurethane resin, the film is opaque or exhibits a drawback such as fish eyes.
- the polyol a mixture comprising polyethylene glycol and polytetramethylene glycol or a mixture comprising polyethylene glycol and an ester of ethylene oxide with adipic acid, the polyols having a molecular weight in the range of from 500 to 3,000.
- the fraction of the ethylene oxide in the polyurethane resin obtained by formulating the polyol, isocyanate and chain extender is held at 7.0 mol/kg or more.
- the polyurethane resin used in the present invention is produced by a one-shot process or a prepolymer process in the absence (bulk polymerization) or presence (solution polymerization) of a solvent.
- the above-described polyurethane resin may be used in the form of a mixture with other urethane resins.
- the other urethane resins include conventional urethane resins having a glass transition temperature of -20°C or below, such as an ether urethane resin, an ester urethane resin, a polycarbonate urethane resin, a urethane resin modified with an amino acid and a urethane resin modified with fluorine.
- the ratio of the water vapor permeability at a high temperature to the water vapor permeability at a low temperature is preferably 1.4 or more from the viewpoint of ensuring the comfortability derived from the release from a sweaty feeling in a high-temperature and high-humidity environment and ensuring the comfortability derived from warmth in a low-temperature environment.
- water vapor permeability (g/m 2 ⁇ 24 hr ⁇ mmHg) used herein is intended to mean a numerical value obtained by dividing the moisture permeability (g/m 2 ⁇ 24 hr) at the measuring temperature by the partial pressure of water vapor (mmHg).
- the expression "at a low temperature” is intended to mean that the temperature within clothes is in the range of from 0 to 20°C
- the expression “at a high temperature” is intended to mean that the temperature within clothes is in the range of from 20 to 50°C.
- Conventional moisture-permeable waterproof woven fabrics having a high moisture permeability have a constant high water vapor permeability ratio, so that at a high temperature they positively release water vapor outside the clothes and, at the same time, the latent heat of water vapor is released outside the clothes also at a low temperature, which easily offers a good comfortability. Since, however, the water vapor permeability is high also at a low temperature, the latent heat of water vapor is released outside the clothes, so that the heat retaining property is poor.
- the moisture permeability (g/m 2 ⁇ 24 hr) was measured according to a method specified in JIS L 1099 A-1.
- conditions of a temperature of 5°C and a relative humidity of 90% were adopted as the low-temperature environment used in the measurement, and conditions of a temperature of 40°C and a relative humidity of 90% were adopted as the high-temperature environment used in the measurement.
- Specific temperature and humidity in the high-temperature environment and the low temperature environment are not particularly limited.
- the temperature range and humidity range within clothes to be controlled may be determined depending upon applications, and the temperature and humidity in each of the high-temperature environment and the low-temperature environment may be determined based on the ranges. Then, selection is effected in such a manner that the ratio of the water vapor permeability at a high temperature to the water vapor permeability at a low temperature becomes high.
- the moisture permeability in a high-temperature environment i.e., at a temperature of 40°C and a relative humidity of 90%
- the moisture permeability in a low-temperature environment i.e., at a temperature of 5°C and a relative humidity of 90%
- the water pressure resistance is preferably 1,000 mmH 2 O or more.
- the temperature at which water vapor is positively released and the temperature at which the heat retaining property is exhibited may be regulated by taking advantage of the glass transition temperature of the polyurethane resin depending upon the applications.
- the glass transition temperature of the polyurethane resin used in the present invention is in the range of from -20 to 20°C from the viewpoint of the comfort of persons during usual work and exercise.
- the moisture-permeable waterproof woven fabric of the present invention having the above-described constitution exhibits excellent moisture permeability in a high-temperature and high-humidity environment and reduces its moisture permeability in a low-temperature environment to exhibit an excellent heat-retaining property, which enables the temperature and humidity within products to be positively controlled.
- a polar organic solvent solution containing the above-described polyurethane resin is coated on at least one surface of a woven fabric preferably at a coverage of 3 to 50 g/m 2 to form a coating which is subjected to solidification and removal of the solvent and then dried.
- the coverage of the polyurethane resin is preferably in the range of from 3 to 10 g/m 2 after drying from the viewpoint of keeping the hand good.
- a polyurethane resin film is further formed by wet coagulation or dry process on the film formed by the above-described method.
- the polar organic solvent used as the solvent for the polyurethane resin mainly from water-soluble polar organic solvents, such as dimethylformamide (hereinafter referred to as "DMF"), dimethylacetamide and N-methylpyrrolidone, from the viewpoint of solubility of the resin in the solvent and ease of removing the solvent.
- DMF dimethylformamide
- isocyanate crosslinking agents, surfactants, etc. serve to form a crosslinked structure in the film by the heat treatment after the formation of the film, which contributes to an improvement in strength and durability of the film.
- the solidification and removal of the solvent may be effected by the conventional wet solidification method.
- An aqueous solution of the above-described solvent and water are preferably used as the coagulation bath.
- the solidification temperature is preferably in the range of from 5 to 50°C from the viewpoint of regulating the diameter of pores formed in the resin film to a suitable range.
- Water is preferably used for removing the solvent.
- the temperature at which the solvent is removed is preferably in the range of from 10 to 80°C.
- the woven fabric is then dried by the conventional method. In this case, the drying temperature is preferably in the range of from 60 to 140°C.
- a water repellency treatment may be effected according to need after drying for the purpose of imparting durable water repellency to the woven fabric.
- water repellency treatment use may be made of known water repellents. Further, in order to improve the quality of the woven fabric product, it is preferred to further subject the woven fabric to finish setting.
- the woven fabric may be subjected to a water repellency treatment or a calendering treatment before it is coated with the resin.
- the resin film formed by the wet process easily becomes porous to provide a moisture-permeable waterproof woven fabric having a good moisture permeability.
- a volatile organic solvent solution containing the above-described polyurethane resin is coated on a release paper preferably at a coverage of 50 to 200 g/m 2 to form a resin film. Then, an adhesive resin is applied onto the resin film and, if necessary, dried at 40 to 150°C. It is then laminated to at least one surface of a woven fabric, and the release paper is peeled off.
- the coverage of the polyurethane resin after drying is preferably in the range of from 10 to 50 g/m 2
- preferred examples of the volatile solvent include toluene, methyl ethyl ketone, isopropyl alcohol and dimethylformamide.
- Ultraviolet absorbers, antioxidants, foaming agents, etc. may be added to the resin solution.
- both a porous resin film and a nonporous resin film can be produced.
- isocyanate crosslinking agents, surfactants, etc. may also be added to the resin solution.
- the isocyanate crosslinking agents serve to form a crosslinked structure in the film by the heat treatment after the formation of the film, which contributes to an improvement in strength and durability of the film.
- a resin film may be applied by the dry process according to the present invention onto the surface of a resin film of a moisture-permeable waterproof woven fabric prepared from a conventional polyurethane resin.
- the waterproof woven fabric prepared by this method has a water pressure resistance of 10,000 mmH 2 O or more.
- the moisture permeability depends upon the temperature. Specifically, when the service temperature is low, the movement of water vapor, that is, the movement of latent heat, is inhibited to maintain the heat retaining property, while when the service temperature is high, water vapor is positively passed through the woven fabric to release latent heat, which prevents occurrence of a sweaty state and a rise in temperature. Therefore, use of the moisture-permeable waterproof woven fabric of the present invention in wind breakers, ski wear, working clothes, shoes, etc.
- clothes that have a waterproofing property, exhibit an excellent heat retaining property when the body is not warmed up yet before exercise or in an early stage of exercise, and a high water vapor permeability when the body is in a warmed state during or after exercise, are less likely to cause a sweaty state, can provide a cool feeling, are comfortable and have good hand.
- the moisture permeability and water pressure resistance were measured respectively in accordance with JIS L 1099 A-1 and JIS L 1092 (by a low water pressure method for products having a water pressure resistance of 2,000 mmH 2 O (1.96kPa) or less and a high water pressure method for products having a water pressure resistance exceeding 2,000 (1.96kPa) mmH 2 O).
- a polyester ponzee woven fabric (75D-72F for both warps and wefts, end spacing: 101 yarns/inch (2.54 cm), pick spacing: 80 yarns/inch (2.54 cm)) was subjected to padding with a 10% aqueous solution of Asahi Guard AG710 as a fluoro water repellent, and the padded woven fabric was dried and cured.
- a polyol was dissolved in DMF at 50°C with stirring, and a diisocyanate was placed therein. The mixture was stirred for about one hr to provide a prepolymer. Then, a chain extender was added thereto dropwise to cause a polymerization reaction, thereby providing a DMF solution of 25% by weight of polyurethane resin.
- MDI as the diisocyanate
- polyethylene glycol having a molecular weight of 2,000 and polyethylene glycol adipate diol having a molecular weight of 1,200 each as the polyol and ethylene glycol as the chain extender were mixed together in a molar ratio of 3.4 : 0.5 : 0.5 : 2.5.
- the glass transition temperature of the resultant polyurethane resin was 0.2°C, and the fraction of ethylene oxide in the polymer was 8.4 mol/kg.
- a resin solution prepared by adding 10 parts by weight of DMF and 1 part by weight of Resamine NE (manufactured by Dainichiseika Color & Chemicals) as an isocyanate crosslinking agent to 100 parts by weight of the above-described solution and mixing them with each other was coated on one surface of the above-described woven fabric at a coverage of 15 g/m 2 , and the coating was solidified in an aqueous solution for 5 min. Thereafter, the solvent was removed with water at 25°C, and the treated woven fabric was washed, dried, subjected to a fluoro oiliness water repellency treatment and then subjected to finish setting at 150°C to provide a coated woven fabric.
- Resamine NE manufactured by Dainichiseika Color & Chemicals
- the coverage of the polyurethane resin after drying was 5 g/m 2 .
- the coated woven fabric thus obtained was subjected to measurement of moisture permeability, water pressure resistance and water vapor permeability ratio (dependency of the moisture permeability upon environment ranging from low-temperature environment to high-temperature environment). The results are given in Table 1.
- a polyester ponzee woven fabric (75D-72F for both warps and wefts, end spacing: 101 yarns/inch (2.54 cm), pick spacing: 80 yarns/inch (2.54 cm)) was subjected to padding with a 10% aqueous solution of Asahi Guard AG 710 as a fluoro water repellent, and the padded woven fabric was dried and cured.
- a polyol was dissolved in DMF at 50°C with stirring, and a diisocyanate was placed therein. The mixture was stirred for about one hr to provide a prepolymer. Then, a chain extender was added thereto dropwise to cause a polymerization reaction, thereby providing a DMF solution of 25% by weight of polyurethane resin.
- MDI as the diisocyanate
- polyethylene glycol having a molecular weight of 2,000 and polyethylene glycol adipate diol having a molecular weight of 1,200 each as the polyol and 1,4-butanediol as the chain extender were mixed together in a molar ratio of 1.2 : 0.7 : 0.2 : 0.2.
- the glass transition temperature of the resultant polyurethane resin was 3.0°C, and the fraction of ethylene oxide in the polymer was 11.3 mol/kg.
- a resin solution prepared by adding 10 parts by weight of DMF and 1 part by weight of Resamine NE (manufactured by Dainichiseika Color & Chemicals) as an isocyanate crosslinking agent to 100 parts by weight of the above-described solution and mixing them with one another was coated on one surface of the above-described woven fabric at a coverage of 15 g/m 2 , and the coating was solidified in an aqueous solution for 5 min. Thereafter, the solvent was removed with water at 25°C, and the treated woven fabric was washed, dried, subjected to a fluoro oiliness water repellency treatment and then subjected to finish setting at 150°C to provide a coated woven fabric.
- Resamine NE manufactured by Dainichiseika Color & Chemicals
- the coverage of the polyurethane resin after drying was 5 g/m 2 .
- the coated woven fabric thus obtained was subjected to measurement of moisture permeability, water pressure resistance and water vapor permeability ratio (dependency of the moisture permeability upon environment ranging from low-temperature environment to high-temperature environment). The results are given in Table 1.
- a polyester ponzee woven fabric (75D-72F for both warps and wefts, end spacing: 101 yarns/inch (2.54 cm), pick spacing: 80 yarns/inch (2.54 cm)) was subjected to padding with a 10% aqueous solution of Asahi Guard AG710 as a fluoro water repellent, and the padded woven fabric was dried and cured.
- a polyol was dissolved in DMF at 50°C with stirring, and a diisocyanate was placed therein. The mixture was stirred for about one hr to provide a prepolymer.- Then, a chain extender was added thereto dropwise to cause a polymerization reaction, thereby providing a DMF solution of 25% by weight of polyurethane resin.
- MDI as the diisocyanate
- polyethylene glycol having a molecular weight of 2,000 and polytetramethylene glycol having a molecular weight of 2,000 each as the polyol and ethylene glycol as the chain extender were mixed together in a molar ratio of 3.3 : 0.5 : 0.5 : 2.4.
- the glass transition temperature of the resultant polyurethane resin was -8.5°C, and the fraction of ethylene oxide in the polymer was 7.4 mol/kg.
- a resin solution prepared by adding 20 parts by weight of methyl ethyl ketone and 80 parts by weight of toluene to 100 parts by weight of the above-described solution and mixing them with one another was coated on a release paper at a coverage of 80 g/m 2 , and the coating was dried at 120°C. Then, a resin solution prepared by adding 60 parts by weight of toluene and 10 parts by weight of Resamine NE (manufactured by Dainichiseika Color & Chemicals) as an isocyanate crosslinking agent was added to 100 parts by weight of an ether polyurethane resin as a binder resin and mixing them with one another was coated on the resultant resin film and laminated on one surface of the above-described woven fabric.
- Resamine NE manufactured by Dainichiseika Color & Chemicals
- the laminate was aged for 24 hr, and the release paper was peeled off to provide a laminate woven fabric.
- the coverage of the polyurethane resin after drying was 15 g/m 2 .
- the coated woven fabric thus obtained was subjected to measurement of moisture permeability, water pressure resistance and the ratio of water vapor permeability at a high temperature to water vapor permeability at a low temperature. The results are given in Table 1.
- a laminate fabric was prepared in the same manner as that of Example 3, except that a polyester knit (a tricot of 30 d and 20 gauge) was used as the fabric, and MDI as the diisocyanate, polyethylene glycol having a molecular weight of 2,000 and polytetraethylene glycol having a molecular weight of 2,000 each as the polyol and ethylene glycol as the chain extender were used in a molar ratio of 3.30 : 0.55 : 0.45 : 2.40.
- the glass transition temperature of the polyurethane resin was -18°C, and the fraction of ethylene oxide in the polymer was 7.8 mol/kg.
- the laminate fabric thus obtained was subjected to measurement of moisture permeability, water pressure resistance and the ratio of water vapor permeability at a high temperature to water vapor permeability at a low temperature. The results are given in Table 1.
- a mixed resin solution having the following composition was coated on one surface of the same fabric as that used in Example 4, and the coating was solidified in an aqueous solution for 5 min. Thereafter, the solvent was removed with water at 25°C, and the coating was then dried to provide a fabric having a porous film at a coverage of 27 g/m 2 .
- Ester polyurethane resin 100 parts Dimethylformamide 80 parts Resamine NE (manufactured by Dainichiseika Color & Chemicals) 1 part
- Example 4 a fabric having a porous film and a nonporous film was prepared using the same resin and method as those of Example 4.
- the laminate fabric thus obtained was subjected to measurement of moisture permeability, water pressure resistance and the ratio of water vapor permeability at a high temperature to water vapor permeability at a low temperature. The results are given in Table 1.
- a coated woven fabric was prepared in the same manner as that of Example 2, except that MDI, polyethylene glycol, polyethylene glycol adipate diol and 1,4-butanediol were used in a molar ratio of 3.3 : 0.3 : 0.7 : 2.4.
- the glass transition temperature of the polyurethane resin was 0.8°C, and the fraction of ethylene oxide in the polymer was 4.54 mol/kg.
- the coated woven fabric thus obtained was subjected to measurement of moisture permeability, water pressure resistance and the ratio of water vapor permeability at a high temperature to water vapor permeability at a low temperature. The results are given in Table 1.
- a coated woven fabric was prepared in the same manner as that of Example 2, except that the polyurethane resin used had a glass transition temperature of -50°C.
- the coated woven fabric thus obtained was subjected to measurement of moisture permeability, water pressure resistance and the ratio of water vapor permeability at a high temperature to water vapor permeability at a low temperature. The results are given in Table 1.
- a coated woven fabric was prepared in the same manner as that of Example 2, except that the polyurethane resin used had a glass transition temperature of -50°C and a high moisture permeability.
- the coated woven fabric thus obtained was subjected to measurement of moisture permeability, water pressure resistance and the ratio of water vapor permeability at a high temperature to water vapor permeability at a low temperature. The results are given in Table 1.
- a laminate fabric was prepared in the same manner as that of Example 4, except that the polyurethane resin used had a glass transition temperature of -50°C.
- the laminate fabric thus obtained was subjected to measurement of moisture permeability, water pressure resistance and the ratio of water vapor permeability at a high temperature to water vapor permeability at a low temperature. The results are given in Table 1.
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Dispersion Chemistry (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
- Laminated Bodies (AREA)
- Polyurethanes Or Polyureas (AREA)
- Synthetic Leather, Interior Materials Or Flexible Sheet Materials (AREA)
Abstract
A moisture-permeable waterproof cloth which is composed of a cloth and, formed on at least one side of the cloth, a resin coating containing a polyurethane resin which is prepared by the reaction among an isocyanate, a polyol and a chain-lenghtening agent, has a glass transition point in the range from -20 to +20 C, and contains at least 7.0 mol/kg of ethylene oxide units. It is produced either by coating at least one side of a cloth with a resin solution containing a polyurethane resin in a polar organic solvent and conducting wet coagulation in a coagulating bath to form a coating film, or by coating a release paper with a resin solution containing a polyurethane resin in a volatile organic solvent to form a resin coating and adhering the coating to at least one side of a cloth.
Description
The present invention relates to a moisture-permeable
waterproof fabric and a process for producing
it. More particularly, the present invention is
concerned with a comfortable moisture-permeable
waterproof fabric, which can control the moisture
permeability and heat retaining property so as to
correspond with required bodily sensations, regarding
warmth and coldness, and a process for producing it.
In particular, it relates to such fabrics having on at
least one surface a polyurethane resin fiber.
Fabrics laminated with polyurethane layers and
processes for producing them are well known. For
example, FR-A-2369815 describes a process for making
polyurethane foam backed carpets for the automobile
industry. The polyurethane may be produced from an
isocyanate, a polyether (obtainable by polymerization
of an epoxide and having a molecular weight of 400 to
10,000) and a chain extender.
DE-A-2431846 discloses a process for laminating a
fabric with a polyurethane coating by means of an
adhesive in which respective solutions of the
polyurethane and adhesive are applied, each solution
containing the same solvent in order to improve the
process. The polyurethane may be produced from an
isocyanate, a polyether (obtainable by polymerization
of an epoxide and having a molecular weight of 600 to
4,000) and a chain extender.
Conventional techniques for producing finished
fabrics having both moisture-permeable and
waterproofing properties were aimed principally at
enhancing the moisture permeability for preventing
humidity during active motion while maintaining the
waterproof property. However, waterproof finished
fabrics having a high moisture permeability provided by
the conventional techniques have poor heat retaining
property due to their high moisture permeability, so
that a person feels cold when the service temperature
is low, that is, when the body is not yet sufficiently
heated before exercise. On the other hand, in
waterproof finished fabrics having a low moisture
permeability, since the moisture permeability is low, a
person feels humid and hot when the service temperature
is high, that is, when the body is in a sufficiently
heated state and sweats profusely during or after
exercise. Therefore, the finished fabrics produced by
the conventional production techniques do not have such
a function as to provide real comfort, that is, a
function that when the service temperature is low, they
exhibit a high heat retaining property and render the
body warm while when the service
temperature is high, they are less likely to retain sweat
and can provide coolness.
An object of the present invention is to provide a
moisture-permeable waterproof woven fabric having real
comfortability, characterised by having a high heat
retaining property when the service temperature is low
while enjoying a high water-vapour permeability to
provide coolness when the service temperature is high,
and a process for producing it.
In order to attain the above-described object, the
present invention provides a moisture-permeable
waterproof woven, knitted or non-woven fabric comprising
a woven, knitted or non-woven fabric substrate and
provided on at least one surface of the fabric substrate,
a resin film comprising a polyurethane resin produced by
reacting an isocyanate component with a polyol component
and a chain extender and having a glass transition
temperature in the range of from -20 to 20°C and an
ethylene oxide unit content of at least 7.0 mol/kg.
Furthermore, the present invention provides a
process for producing a moisture-permeable waterproof
fabric, comprising the steps of: coating at least one
surface of a woven, knitted or non-woven fabric substrate
with a solution of a resin in a polar organic solvent,
the resin comprising a polyurethane resin produced by
reacting an isocyanate component with a polyol component
and a chain extender and having a glass transition
temperature in the range of from -20 to 20°C and an
ethylene oxide unit content of at least 7.0 mol/kg, and
subjecting the coating to wet solidification in a
coagulation bath to form a film, or coating a release
paper with the above-described solution of the resin in a
volatile organic solvent to form a film and adhering the
film on at least one surface of a woven fabric.
The best mode for carrying out the invention is now
described.
The fabric useful for the present invention may
comprise a chemical fiber, such as a polyester,
polyamide, acrylic or rayon fiber, a natural fiber, such
as cotton or wool, or a mixture thereof. They may be in
the form of any of a woven fabric, a knitted fabric and a nonwoven
fabric.
In the polyurethane resin used in the present
invention and produced by reacting an isocyanate component with a
polyol component and a chain extender, a component having a rigid
structure serving to suppress the molecular motion is
used for constituting the polyurethane resin to bring the
glass transition temperature of the polyurethane resin to
the range of from -20 to 20°C, thereby rendering the
moisture permeability of the woven fabric highly
dependent upon the temperature.
In the production of the polyurethane resin useful
for the present invention, known isocyanates commonly
used in polyurethane may be used as the isocyanate
component. Preferred examples thereof include 4,4'-diphenylmethane
diisocyanate (MDI), hydrogenated MDI,
isophorone diisocyanate, 1,3-xylene diisocyanate, 2,4-tolylene
diisocyanate and m-phenylene diisocyanate. They
may be used alone or in the form of a mixture of two or
more of them. MDI and hydrogenated MDI are still
preferred from the viewpoint of rigidity of the molecular
structure.
The chain extender may also be one known in the
art. Preferred examples thereof include ethylene glycol,
propylene glycol, 1,4-butanediol, 1,6-hexanediol,
ethylenediamine, trimethylenediamine, isophoronediamine
and water. They may be used alone or in the form of a
mixture of two or more of them. Ethylene glycol,
propylene glycol and water are particularly preferred
from the viewpoint of rigidity of the molecular
structure.
The polyol component may be one known in the art,
and examples thereof include high-molecular weight diols,
such as polyethylene glycol which is a product of
addition homopolymerization of ethylene oxide, an
ethylene oxide adduct of tetrahydrofuran which is a
copolymer of ethylene oxide with another compound, an
ethylene oxide adduct of bisphenol A, a condensate of
adipic acid with ethylene oxide and an ethylene oxide
adduct of polybutylene glycol adipate diol or
polypropylene glycol adipate diol, and high-molecular
weight diols not containing ethylene oxide, such as
polytetramethylene glycol, polypropylene ether glycol,
poly-ε-caprolactone glycol, polybutyrolactone glycol,
polypropylene glycol adipate diol and polybutylene glycol
adipate diol. They may be used alone or in the form of a
mixture of two or more of them.
The polyol preferably has a molecular weight in the
range of from 500 to 3,000. When the molecular weight is
less than 500, the elastomeric performance of the
resultant polyurethane resin is unsatisfactory, which
results in poor durability during use. On the other
hand, when the molecular weight is more than 3,000,
conditions for synthesis are limited, which leads to a
problem that when a film is formed from the resultant
polyurethane resin, the film is opaque or exhibits a
drawback such as fish eyes.
In the present invention, it is particularly
preferred to use as the polyol a mixture comprising
polyethylene glycol and polytetramethylene glycol or a
mixture comprising polyethylene glycol and an ester of
ethylene oxide with adipic acid, the polyols having a
molecular weight in the range of from 500 to 3,000.
In the present invention, the fraction of the
ethylene oxide in the polyurethane resin obtained by
formulating the polyol, isocyanate and chain extender is
held at 7.0 mol/kg or more.
The polyurethane resin used in the present
invention is produced by a one-shot process or a
prepolymer process in the absence (bulk polymerization)
or presence (solution polymerization) of a solvent.
In the present invention, the above-described
polyurethane resin may be used in the form of a mixture
with other urethane resins. Examples of the other
urethane resins include conventional urethane resins
having a glass transition temperature of -20°C or below,
such as an ether urethane resin, an ester urethane resin,
a polycarbonate urethane resin, a urethane resin modified
with an amino acid and a urethane resin modified with
fluorine.
In the products obtained from the fabric of
the present invention, particularly articles of clothing,
the ratio of the water vapor permeability at a high
temperature to the water vapor permeability at a low
temperature is preferably 1.4 or more from the viewpoint
of ensuring the comfortability derived from the release
from a sweaty feeling in a high-temperature and high-humidity
environment and ensuring the comfortability
derived from warmth in a low-temperature environment.
The term "water vapor permeability (g/m2·24 hr·mmHg)"
used herein is intended to mean a numerical value obtained
by dividing the moisture permeability (g/m2·24 hr) at the
measuring temperature by the partial pressure of water
vapor (mmHg). Further, the expression "at a low
temperature" is intended to mean that the temperature
within clothes is in the range of from 0 to 20°C, and the
expression "at a high temperature" is intended to mean
that the temperature within clothes is in the range of
from 20 to 50°C. Conventional moisture-permeable
waterproof woven fabrics having a high moisture
permeability have a constant high water vapor
permeability ratio, so that at a high temperature they
positively release water vapor outside the clothes and,
at the same time, the latent heat of water vapor is
released outside the clothes also at a low temperature,
which easily offers a good comfortability. Since,
however, the water vapor permeability is high also at a
low temperature, the latent heat of water vapor is
released outside the clothes, so that the heat retaining
property is poor. On the other hand, conventional
moisture-permeable waterproof woven fabrics having a low
moisture permeability have a constant low water vapor
permeability. Therefore, at a low temperature the water
vapor is not significantly released outside the clothes
and accumulates as latent heat within the clothes to
provide a heat retaining property, whereas at a high
temperature the clothes are likely to cause a sweaty or
sticky feeling due to the low moisture permeability.
The higher the water vapor permeability at a high
temperature, the lower the water vapor permeability at a
low temperature and the higher the water vapor
permeability ratio, the larger the temperature dependence
of the moisture permeability of the moisture-permeable
waterproof woven fabric, that is, the higher the tendency
that at a high temperature the water vapor is positively
released to prevent the inside of the clothes from
becoming stuffy while at a low temperature the permeation
of water vapor is inhibited to exhibit a heat retaining
property.
In the present invention, the moisture permeability
(g/m2·24 hr) was measured according to a method specified
in JIS L 1099 A-1. In this connection, conditions of a
temperature of 5°C and a relative humidity of 90% were
adopted as the low-temperature environment used in the
measurement, and conditions of a temperature of 40°C and
a relative humidity of 90% were adopted as the high-temperature
environment used in the measurement.
Specific temperature and humidity in the high-temperature
environment and the low temperature
environment are not particularly limited. In this case,
the temperature range and humidity range within clothes
to be controlled may be determined depending upon
applications, and the temperature and humidity in each of
the high-temperature environment and the low-temperature
environment may be determined based on the ranges. Then,
selection is effected in such a manner that the ratio of
the water vapor permeability at a high temperature to the
water vapor permeability at a low temperature becomes
high.
In the moisture-permeable waterproof woven fabric
of the present invention, the moisture permeability in a
high-temperature environment, i.e., at a temperature of
40°C and a relative humidity of 90%, is preferably
8,000 g/m2·24 hr or more, the moisture permeability in a
low-temperature environment, i.e., at a temperature of
5°C and a relative humidity of 90%, is preferably less
than 1,000 g/m2·24 hr or more, and the water pressure
resistance is preferably 1,000 mmH2O or more.
The temperature at which water vapor is positively
released and the temperature at which the heat retaining
property is exhibited may be regulated by taking
advantage of the glass transition temperature of the
polyurethane resin depending upon the applications. The
glass transition temperature of the polyurethane resin
used in the present invention is in the range of from -20
to 20°C from the viewpoint of the comfort of persons
during usual work and exercise.
The moisture-permeable waterproof woven fabric of
the present invention having the above-described
constitution exhibits excellent moisture permeability in
a high-temperature and high-humidity environment and
reduces its moisture permeability in a low-temperature
environment to exhibit an excellent heat-retaining
property, which enables the temperature and humidity
within products to be positively controlled.
The process for producing the moisture-permeable
waterproof woven fabric of the present invention will now
be described.
In the production of the moisture-permeable
waterproof woven fabric by the wet process, for example,
a polar organic solvent solution containing the above-described
polyurethane resin is coated on at least one
surface of a woven fabric preferably at a coverage of 3
to 50 g/m2 to form a coating which is subjected to
solidification and removal of the solvent and then dried.
In this case, the coverage of the polyurethane resin is
preferably in the range of from 3 to 10 g/m2 after drying
from the viewpoint of keeping the hand good. In
applications where importance is given to the water
pressure resistance, a polyurethane resin film is further
formed by wet coagulation or dry process on the film
formed by the above-described method. It is preferred to
select the polar organic solvent used as the solvent for
the polyurethane resin mainly from water-soluble polar
organic solvents, such as dimethylformamide (hereinafter
referred to as "DMF"), dimethylacetamide and N-methylpyrrolidone,
from the viewpoint of solubility of
the resin in the solvent and ease of removing the
solvent. Further, it is also possible to add isocyanate
crosslinking agents, surfactants, etc. to the resin
solution. The isocyanate crosslinking agents serve to
form a crosslinked structure in the film by the heat
treatment after the formation of the film, which
contributes to an improvement in strength and durability
of the film.
The solidification and removal of the solvent may
be effected by the conventional wet solidification
method. An aqueous solution of the above-described
solvent and water are preferably used as the coagulation
bath. The solidification temperature is preferably in
the range of from 5 to 50°C from the viewpoint of
regulating the diameter of pores formed in the resin film
to a suitable range. Water is preferably used for
removing the solvent. The temperature at which the
solvent is removed is preferably in the range of from 10
to 80°C. The woven fabric is then dried by the
conventional method. In this case, the drying
temperature is preferably in the range of from 60 to
140°C. Further, a water repellency treatment may be
effected according to need after drying for the purpose
of imparting durable water repellency to the woven
fabric. In the water repellency treatment, use may be
made of known water repellents. Further, in order to
improve the quality of the woven fabric product, it is
preferred to further subject the woven fabric to finish
setting. The woven fabric may be subjected to a water
repellency treatment or a calendering treatment before it
is coated with the resin.
The resin film formed by the wet process easily
becomes porous to provide a moisture-permeable waterproof
woven fabric having a good moisture permeability.
In the production of the moisture-permeable
waterproof woven fabric by the dry process, for example,
a volatile organic solvent solution containing the above-described
polyurethane resin is coated on a release paper
preferably at a coverage of 50 to 200 g/m2 to form a
resin film. Then, an adhesive resin is applied onto the
resin film and, if necessary, dried at 40 to 150°C. It
is then laminated to at least one surface of a woven
fabric, and the release paper is peeled off. The
coverage of the polyurethane resin after drying is
preferably in the range of from 10 to 50 g/m2, and
preferred examples of the volatile solvent include
toluene, methyl ethyl ketone, isopropyl alcohol and
dimethylformamide. Ultraviolet absorbers, antioxidants,
foaming agents, etc. may be added to the resin solution.
In the dry process, both a porous resin film and a
nonporous resin film can be produced. Further,
isocyanate crosslinking agents, surfactants, etc. may
also be added to the resin solution. The isocyanate
crosslinking agents serve to form a crosslinked structure
in the film by the heat treatment after the formation of
the film, which contributes to an improvement in strength
and durability of the film.
Further, a resin film may be applied by the dry
process according to the present invention onto the
surface of a resin film of a moisture-permeable
waterproof woven fabric prepared from a conventional
polyurethane resin. The waterproof woven fabric prepared
by this method has a water pressure resistance of
10,000 mmH2O or more.
In the moisture-permeable waterproof woven fabric
according to the present invention, the moisture
permeability depends upon the temperature. Specifically,
when the service temperature is low, the movement of
water vapor, that is, the movement of latent heat, is
inhibited to maintain the heat retaining property, while
when the service temperature is high, water vapor is
positively passed through the woven fabric to release
latent heat, which prevents occurrence of a sweaty state
and a rise in temperature. Therefore, use of the
moisture-permeable waterproof woven fabric of the present
invention in wind breakers, ski wear, working clothes,
shoes, etc. can provide clothes that have a waterproofing
property, exhibit an excellent heat retaining property
when the body is not warmed up yet before exercise or in
an early stage of exercise, and a high water vapor
permeability when the body is in a warmed state during or
after exercise, are less likely to cause a sweaty state,
can provide a cool feeling, are comfortable and have good
hand.
The present invention will now be described in more
detail with reference to the following Examples.
In the following Examples, the moisture
permeability and water pressure resistance were measured
respectively in accordance with JIS L 1099 A-1 and JIS L
1092 (by a low water pressure method for products having
a water pressure resistance of 2,000 mmH2O (1.96kPa) or less and a
high water pressure method for products having a water
pressure resistance exceeding 2,000 (1.96kPa) mmH2O).
A polyester ponzee woven fabric (75D-72F for both
warps and wefts, end spacing: 101 yarns/inch (2.54 cm), pick
spacing: 80 yarns/inch (2.54 cm)) was subjected to padding with a
10% aqueous solution of Asahi Guard AG710 as a fluoro
water repellent, and the padded woven fabric was dried
and cured.
A polyol was dissolved in DMF at 50°C with
stirring, and a diisocyanate was placed therein. The
mixture was stirred for about one hr to provide a
prepolymer. Then, a chain extender was added thereto
dropwise to cause a polymerization reaction, thereby
providing a DMF solution of 25% by weight of polyurethane
resin. MDI as the diisocyanate, polyethylene glycol
having a molecular weight of 2,000 and polyethylene
glycol adipate diol having a molecular weight of 1,200
each as the polyol and ethylene glycol as the chain
extender were mixed together in a molar ratio of 3.4 :
0.5 : 0.5 : 2.5. The glass transition temperature of the
resultant polyurethane resin was 0.2°C, and the fraction
of ethylene oxide in the polymer was 8.4 mol/kg.
A resin solution prepared by adding 10 parts by
weight of DMF and 1 part by weight of Resamine NE
(manufactured by Dainichiseika Color & Chemicals) as an
isocyanate crosslinking agent to 100 parts by weight of
the above-described solution and mixing them with each
other was coated on one surface of the above-described
woven fabric at a coverage of 15 g/m2, and the coating
was solidified in an aqueous solution for 5 min.
Thereafter, the solvent was removed with water at 25°C,
and the treated woven fabric was washed, dried, subjected
to a fluoro oiliness water repellency treatment and then
subjected to finish setting at 150°C to provide a coated
woven fabric. The coverage of the polyurethane resin
after drying was 5 g/m2. The coated woven fabric thus
obtained was subjected to measurement of moisture
permeability, water pressure resistance and water vapor
permeability ratio (dependency of the moisture
permeability upon environment ranging from low-temperature
environment to high-temperature environment).
The results are given in Table 1.
A polyester ponzee woven fabric (75D-72F for both
warps and wefts, end spacing: 101 yarns/inch (2.54 cm), pick
spacing: 80 yarns/inch (2.54 cm)) was subjected to padding with a
10% aqueous solution of Asahi Guard AG 710 as a fluoro
water repellent, and the padded woven fabric was dried
and cured.
A polyol was dissolved in DMF at 50°C with
stirring, and a diisocyanate was placed therein. The
mixture was stirred for about one hr to provide a
prepolymer. Then, a chain extender was added thereto
dropwise to cause a polymerization reaction, thereby
providing a DMF solution of 25% by weight of polyurethane
resin. MDI as the diisocyanate, polyethylene glycol
having a molecular weight of 2,000 and polyethylene
glycol adipate diol having a molecular weight of 1,200
each as the polyol and 1,4-butanediol as the chain
extender were mixed together in a molar ratio of 1.2 :
0.7 : 0.2 : 0.2. The glass transition temperature of the
resultant polyurethane resin was 3.0°C, and the fraction
of ethylene oxide in the polymer was 11.3 mol/kg.
A resin solution prepared by adding 10 parts by
weight of DMF and 1 part by weight of Resamine NE
(manufactured by Dainichiseika Color & Chemicals) as an
isocyanate crosslinking agent to 100 parts by weight of
the above-described solution and mixing them with one
another was coated on one surface of the above-described
woven fabric at a coverage of 15 g/m2, and the coating
was solidified in an aqueous solution for 5 min.
Thereafter, the solvent was removed with water at 25°C,
and the treated woven fabric was washed, dried, subjected
to a fluoro oiliness water repellency treatment and then
subjected to finish setting at 150°C to provide a coated
woven fabric. The coverage of the polyurethane resin
after drying was 5 g/m2. The coated woven fabric thus
obtained was subjected to measurement of moisture
permeability, water pressure resistance and water vapor
permeability ratio (dependency of the moisture
permeability upon environment ranging from low-temperature
environment to high-temperature environment).
The results are given in Table 1.
A polyester ponzee woven fabric (75D-72F for both
warps and wefts, end spacing: 101 yarns/inch (2.54 cm), pick
spacing: 80 yarns/inch (2.54 cm)) was subjected to padding with a
10% aqueous solution of Asahi Guard AG710 as a fluoro
water repellent, and the padded woven fabric was dried
and cured.
A polyol was dissolved in DMF at 50°C with
stirring, and a diisocyanate was placed therein. The
mixture was stirred for about one hr to provide a
prepolymer.- Then, a chain extender was added thereto
dropwise to cause a polymerization reaction, thereby
providing a DMF solution of 25% by weight of polyurethane
resin. MDI as the diisocyanate, polyethylene glycol
having a molecular weight of 2,000 and polytetramethylene
glycol having a molecular weight of 2,000 each as the
polyol and ethylene glycol as the chain extender were
mixed together in a molar ratio of 3.3 : 0.5 : 0.5 : 2.4.
The glass transition temperature of the resultant
polyurethane resin was -8.5°C, and the fraction of
ethylene oxide in the polymer was 7.4 mol/kg.
A resin solution prepared by adding 20 parts by
weight of methyl ethyl ketone and 80 parts by weight of
toluene to 100 parts by weight of the above-described
solution and mixing them with one another was coated on a
release paper at a coverage of 80 g/m2, and the coating
was dried at 120°C. Then, a resin solution prepared by
adding 60 parts by weight of toluene and 10 parts by
weight of Resamine NE (manufactured by Dainichiseika
Color & Chemicals) as an isocyanate crosslinking agent
was added to 100 parts by weight of an ether polyurethane
resin as a binder resin and mixing them with one another
was coated on the resultant resin film and laminated on
one surface of the above-described woven fabric. The
laminate was aged for 24 hr, and the release paper was
peeled off to provide a laminate woven fabric. The
coverage of the polyurethane resin after drying was
15 g/m2. The coated woven fabric thus obtained was
subjected to measurement of moisture permeability, water
pressure resistance and the ratio of water vapor
permeability at a high temperature to water vapor
permeability at a low temperature. The results are given
in Table 1.
A laminate fabric was prepared in the same
manner as that of Example 3, except that a polyester knit
(a tricot of 30 d and 20 gauge) was used as the
fabric, and MDI as the diisocyanate, polyethylene glycol
having a molecular weight of 2,000 and polytetraethylene
glycol having a molecular weight of 2,000 each as the
polyol and ethylene glycol as the chain extender were
used in a molar ratio of 3.30 : 0.55 : 0.45 : 2.40. The
glass transition temperature of the polyurethane resin
was -18°C, and the fraction of ethylene oxide in the
polymer was 7.8 mol/kg. The laminate fabric thus
obtained was subjected to measurement of moisture
permeability, water pressure resistance and the ratio of
water vapor permeability at a high temperature to water
vapor permeability at a low temperature. The results are
given in Table 1.
A mixed resin solution having the following
composition was coated on one surface of the same
fabric as that used in Example 4, and the coating was
solidified in an aqueous solution for 5 min. Thereafter,
the solvent was removed with water at 25°C, and the
coating was then dried to provide a fabric having a
porous film at a coverage of 27 g/m2.
| Ester polyurethane resin | 100 parts |
| Dimethylformamide | 80 parts |
| Resamine NE (manufactured by Dainichiseika Color & Chemicals) | 1 part |
Then, a fabric having a porous film and a
nonporous film was prepared using the same resin and
method as those of Example 4. The laminate fabric
thus obtained was subjected to measurement of moisture
permeability, water pressure resistance and the ratio of
water vapor permeability at a high temperature to water
vapor permeability at a low temperature. The results are
given in Table 1.
A coated woven fabric was prepared in the same
manner as that of Example 2, except that MDI,
polyethylene glycol, polyethylene glycol adipate diol and
1,4-butanediol were used in a molar ratio of 3.3 : 0.3 :
0.7 : 2.4. The glass transition temperature of the
polyurethane resin was 0.8°C, and the fraction of
ethylene oxide in the polymer was 4.54 mol/kg. The
coated woven fabric thus obtained was subjected to
measurement of moisture permeability, water pressure
resistance and the ratio of water vapor permeability at a
high temperature to water vapor permeability at a low
temperature. The results are given in Table 1.
A coated woven fabric was prepared in the same
manner as that of Example 2, except that the polyurethane
resin used had a glass transition temperature of -50°C.
The coated woven fabric thus obtained was subjected to
measurement of moisture permeability, water pressure
resistance and the ratio of water vapor permeability at a
high temperature to water vapor permeability at a low
temperature. The results are given in Table 1.
A coated woven fabric was prepared in the same
manner as that of Example 2, except that the polyurethane
resin used had a glass transition temperature of -50°C
and a high moisture permeability. The coated woven
fabric thus obtained was subjected to measurement of
moisture permeability, water pressure resistance and the
ratio of water vapor permeability at a high temperature
to water vapor permeability at a low temperature. The
results are given in Table 1.
A laminate fabric was prepared in the same
manner as that of Example 4, except that the polyurethane
resin used had a glass transition temperature of -50°C.
The laminate fabric thus obtained was subjected to
measurement of moisture permeability, water pressure
resistance and the ratio of water vapor permeability at a
high temperature to water vapor permeability at a low
temperature. The results are given in Table 1.
Claims (9)
- A moisture-permeable waterproof woven, knitted or non-woven fabric comprising a woven, knitted or non-woven fabric substrate and, provided on at least one surface of the said substrate, a resin film comprising a polyurethane resin produced by reaching an isocyanate component with a polyol component and a chain extender and having a glass transition temperature in the range of from -20 to 20°C and an ethylene oxide unit content of at least 7.0 mol/kg.
- A fabric according to claim 1, wherein the polyol component comprises a mixture comprising polyethylene glycol and polytetramethyl glycol, the polyols having a molecular weight in the range of from 500 to 3,000.
- A fabric according to claim 1, wherein the polyol component comprises a mixture comprising polyethylene glycol and an ester of ethylene oxide with adipic acid, the polyols having a molecular weight in the range of from 500 to 3,000.
- A fabric according to any one of claims 1 to 3, wherein the resin film is porous.
- A fabric according to any one of claims 1 to 3, wherein the resin film is nonporous.
- A fabric according to any one of claims 1 to 5, having a ratio of water vapour permeability at a high temperature to water vapour permeability at a low temperature of 1.4 or higher.
- Fabric according to any one of claims 1 to 5, having a moisture permeability in a low-temperature environment of less than 1,000 g/m2.24 hr and a moisture permeability in a high-temperature environment of 8,000 g/m2.24hr or more.
- A process for producing a moisture-permeable waterproof fabric, comprising the steps of: coating at least one surface of a woven, knitted or non-woven fabric substrate with a solution of a resin in a polar organic solvent, the resin comprising a polyurethane resin produced by reacting an isocyanate component with a polyol component and a chain extender and having a glass transition temperature in the range of from -20 to 20°C and an ethylene oxide unit content of at least 7.0 mol/kg, and subjecting the coating to wet solidification in a coagulation bath to form a film.
- A process for producing a moisture-permeable waterproof fabric, comprising the steps of: (1) coating release paper with a solution of a resin in a polar organic solvent to form a resin film, the resin comprising a polyurethane resin produced by reacting an isocyanate component with a polyol component and a chain extender and having a glass transition temperature in the range of from-20 to 20°C and an ethylene oxid unit content of at least 7.0 mol/kg, and (2) adhering said resin film to at least one surface of a woven, knitted or non-woven fabric substrate with an adhesive thereby forming a laminate of the said resin, adhesive and substrate.
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP16097892 | 1992-06-19 | ||
| JP160978/92 | 1992-06-19 | ||
| JP20672092 | 1992-08-03 | ||
| JP206720/92 | 1992-08-03 | ||
| PCT/JP1993/000827 WO1994000631A1 (en) | 1992-06-19 | 1993-06-18 | Moisture-permeable waterproof cloth and production thereof |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| EP0603410A1 EP0603410A1 (en) | 1994-06-29 |
| EP0603410A4 EP0603410A4 (en) | 1996-04-03 |
| EP0603410B1 true EP0603410B1 (en) | 1998-09-02 |
Family
ID=26487275
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP93913547A Expired - Lifetime EP0603410B1 (en) | 1992-06-19 | 1993-06-18 | Moisture-permeable waterproof cloth and production thereof |
Country Status (5)
| Country | Link |
|---|---|
| EP (1) | EP0603410B1 (en) |
| KR (1) | KR960004914B1 (en) |
| DE (1) | DE69320774T2 (en) |
| TW (1) | TW242659B (en) |
| WO (1) | WO1994000631A1 (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6348422B1 (en) | 1997-10-23 | 2002-02-19 | Komatsu Seiren Co., Ltd. | Moisture-permeable waterproof fabric, and moisture permeable resin film backed with release paper to be used for the production of the fabric |
| JP4949066B2 (en) * | 2007-02-21 | 2012-06-06 | 帝人ファイバー株式会社 | Waterproof and breathable fabric for clothing |
| JP5350316B2 (en) * | 2010-05-14 | 2013-11-27 | 小松精練株式会社 | Durable polyurethane resin composition for moisture permeable waterproof sheet, moisture permeable waterproof sheet and method for producing the same |
| KR102298944B1 (en) * | 2014-02-06 | 2021-09-06 | 고마쓰 마테레 가부시키가이샤 | Waterproof fabric and textile product employing same |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2431846C3 (en) * | 1974-07-02 | 1979-01-11 | Bayer Ag, 5090 Leverkusen | Process for coating textile, web-shaped substrates by the reverse process with polyurethane solutions |
| DE2748085A1 (en) * | 1976-11-04 | 1978-05-18 | Mobay Chemical Corp | PROCESS FOR THE PRODUCTION OF CARPET BACKING COATINGS |
| JPS59158252A (en) * | 1983-03-01 | 1984-09-07 | ジヤパンゴアテツクス株式会社 | Waterproof material of excellent moisture permeability |
| JPS59199869A (en) * | 1983-04-25 | 1984-11-13 | 旭化成株式会社 | Production of fiber product |
| JPS61245376A (en) * | 1985-04-23 | 1986-10-31 | セイコ−化成株式会社 | Moisture permeable water-proof cloth |
| DE3800434A1 (en) * | 1988-01-09 | 1989-07-20 | Bayer Ag | HEAT-CURABLE COATING COMPOSITION BASED ON POLYURETHANE URBAN |
| JPH0268366A (en) * | 1988-09-02 | 1990-03-07 | Kanebo Ltd | Coated cloth of dry touch |
| JPH03294581A (en) * | 1990-04-12 | 1991-12-25 | Seikoh Chem Co Ltd | Production of coated cloth |
| JP3074335B2 (en) * | 1991-06-12 | 2000-08-07 | ユニチカ株式会社 | Moisture-permeable waterproof fabric and method for producing the same |
-
1993
- 1993-06-18 EP EP93913547A patent/EP0603410B1/en not_active Expired - Lifetime
- 1993-06-18 KR KR1019940700485A patent/KR960004914B1/en not_active IP Right Cessation
- 1993-06-18 WO PCT/JP1993/000827 patent/WO1994000631A1/en active IP Right Grant
- 1993-06-18 DE DE69320774T patent/DE69320774T2/en not_active Expired - Fee Related
- 1993-06-19 TW TW82104955A patent/TW242659B/zh not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| EP0603410A1 (en) | 1994-06-29 |
| EP0603410A4 (en) | 1996-04-03 |
| KR960004914B1 (en) | 1996-04-17 |
| DE69320774T2 (en) | 1999-01-21 |
| DE69320774D1 (en) | 1998-10-08 |
| TW242659B (en) | 1995-03-11 |
| WO1994000631A1 (en) | 1994-01-06 |
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