Classifications

• • 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
• • 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
• • 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 method for producing the same. More specifically, the present invention relates to a comfortable moisture-permeable waterproof fabric capable of controlling moisture permeability and heat retention in accordance with the sensation of cold and heat, and a method for producing the same. Background art
• the mainstream of manufacturing technology for processed fabrics with moisture permeability and waterproofness was to increase the moisture permeability to release moisture during activities while maintaining waterproofness.
• the waterproofed cloth with high moisture permeability obtained by the conventional technology can be used even when the operating temperature is low, in other words, even when the body is not warm before exercise or at the beginning of exercise. , Low heat retention due to high moisture permeability, cold.
• a waterproof fabric with low moisture permeability can be used at high operating temperatures.In other words, even when the body warms up during or after exercise and has a large amount of sweat, the moisture permeability is low, and the moisture is low. Easy and hot. Therefore, the work cloth obtained by the conventional manufacturing technology has the function of real comfort, that is, the function of having high heat retention and warm when the operating temperature is low, and the function of preventing stuffiness and cooling when the operating temperature is high. is not. Disclosure of the invention
• the present invention is rich in heat retention when the use temperature is low, has high water vapor permeability when the use temperature is high, and is durable and cool. It is an object of the present invention to provide a moisture-permeable waterproof fabric having true comfort and a method for producing the same.
• the present invention comprises reacting an isocyanate, a polyol and a chain extender, having a glass transition point in the range of 120 ° C to 20 ° C. Also provided is a moisture-permeable waterproof fabric comprising a resin film containing a urethane resin having ethylene oxide units of 7.0 mol / kg provided on at least one side of the fabric.
• the present invention also comprises reacting an isocyanate, a polyol and a chain extender, having a glass transition point in the range of 120 ° C. to 20 ° C. and at least 7.0 moles.
• a resin solution of a polar organic solvent containing a polyurethane resin having an ethylene oxide unit of Z kg is applied to at least one surface of the fabric, and wet-solidified in a coagulation bath to form a film or to contain the resin.
• a method for producing a moisture-permeable waterproof fabric comprising: applying a resin solution of a volatile organic solvent onto release paper to form a resin film, and then adhering the resin film to at least one surface of the fabric.
• the material of the fabric useful in the present invention may be a synthetic fiber such as polyester, polyamide or acryl or rayon, a natural fiber such as cotton or wool, or a mixture of these. They may be in any form of woven, knitted or non-woven fabric.
• the polyurethane resin used in the present invention which is obtained by reacting an isocyanate, a polyol and a chain extender, has a glass transition using a component having a rigid structure that suppresses molecular mobility as a component thereof.
• the point is in the range of 120 ° C to 20 ° C, and its moisture permeability has high temperature dependence.
• an isocyanate Known components commonly used for polyurethanes can be used as the components. Preference is given, for example, to 4,4'-diphenylmethanediisocyanate (MDI), hydrogenated MDI, isophoronediisocyanate, 1,3-xylylenediisocyanate , 2, 4 _ tri-range isocyanate, m-phenylene isocyanate, etc., which can be used alone or as a mixture of two or more kinds. . From the viewpoint of rigidity of the molecular structure, MDI and hydrogenated MDI are more preferable.
• MDI 4,4'-diphenylmethanediisocyanate
• hydrogenated MDI isophoronediisocyanate
• 1,3-xylylenediisocyanate 1,3-xylylenediisocyanate
• 2, 4 _ tri-range isocyanate 1,3-xylylenediisocyanate
• chain extenders can also be used.
• preferred chain extenders include ethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol, ethylenediaminetrimethylenediamine, isophoronediamine, Water and the like can be used, and these can be used alone or as a mixture of two or more. From the viewpoint of the rigidity of the molecular structure, ethylene glycol, propylene glycol and water are particularly preferred.
• polyol components can be used, for example, poly (ethylene glycol), which is an addition polymer of ethylene oxide alone, and a copolymer of ethylene oxide and another compound.
• Ethylene oxide adduct of tetrahydrofuran, ethylene oxide adduct of bisphenol A, condensate of adipic acid and ethylene oxide, polybutylene glycol adipate diol and polypropylene glycol adduct Ethylene oxide-containing high molecular weight diols such as ethylene oxide adducts of diols, as well as polytetramethylene glycol, polypropylene ether glycol, poly ⁇ -caprolactone glycol, and polybutyrolactone glycol , Polypropylene glycol adjuvant Ethylene oxide-free high-molecular diols such as diols and polybutylene glycol adducts Is mentioned. These can be used alone or as a mixture of two or more.
• Polyol preferably has a molecular weight of 50,000 to 300,000.If the molecular weight is less than 50,000, the resulting polyurethane resin has sufficient elastomer performance. Otherwise, the durability in use may be poor. In addition, when the molecular weight is more than 300, the synthesis conditions are restricted, and when the obtained polyurethane resin is formed into a film, it becomes opaque or fish-eye-like foreign matter. The problem of liability to occur.
• the polyol is a mixture of polyethylene glycol and polytetramethylene glycol or a mixture of esters of polyethylene glycol, ethylene oxide and adipic acid, and
• those having a molecular weight in the range of 500 to 300.
• the ethylene oxide fraction in the polyurethan resin obtained by the compounding formulation of these polyols with the isocyanate and the chain extender is 7.0 mol / kg or more. Will be retained.
• the polyurethane resin used in the present invention is produced by a wanshot method or a prepolymer method in the absence of a solvent (bulk polymerization) or in a solvent (solution polymerization).
• the above-mentioned polyurethane resin may be used as a mixture with another urethane resin.
• Other urethane resins include, for example, ordinary ether-based resins, ester-based urethane resins, and polycarbonate-based resins having a glass transition point of 120 ° C or less. Examples include a urethane resin, an amino acid-modified urethane resin, and a fluorine-modified urethane resin.
• the products obtained from the fabric of the present invention, especially clothing, are high temperature and high humidity.
• the water vapor transmission rate at high temperature and the water vapor transmission rate at low temperature Preferably, the ratio is at least 1.4.
• the water vapor transmission rate (gZm 2 ⁇ 24 hrs ⁇ mm H g) is the moisture permeability (gZm 2 ⁇ 24 hrs) at the measurement temperature divided by the water vapor partial pressure (mmH g) at the measurement temperature. It is a numerical value.
• High temperature is 0 ° C to 20 ° C in clothing temperature, and high temperature is 20 ° C to 50 ° C in clothing temperature.
• This ratio of water vapor transmission rate shows a constant high value with the conventional high-permeability water-permeable waterproof fabric.
• water vapor is actively released to the outside of the clothes, and at the same time, latent heat of water vapor is discharged outside the clothes.
• latent heat of water vapor is discharged outside the clothes.
• the water vapor permeability of a conventional low-moisture-permeable, moisture-permeable waterproof fabric shows a constant low value. Therefore, at low temperatures, water vapor is hardly released to the outside of the clothes, so it is accumulated as latent heat in the clothes and has heat retention properties.
• the moisture permeability is small, so that stuffiness and stickiness tend to occur.
• the moisture permeability (g Zm 2 ⁇ 2 4 hrs ⁇ perform measurement in accordance with JISL 1 0 9 9 A- 1 method, adopted as a low-temperature environment temperature 5 ° C, relative humidity 90% A temperature of 40 ° C and a relative humidity of 90% were adopted for the high-temperature environment.
• the specific temperature and humidity in the high-temperature environment and the low-temperature environment are not particularly limited. Determine the range of humidity, and determine the temperature and humidity in high and low temperature environments. Then, the ratio of the water vapor transmission rate at high temperature to the water vapor transmission rate at low temperature should be large.
• the moisture permeability at a temperature of 40 ° C. and a relative humidity of 90% in a high-temperature environment is preferably 800 g / m 2 ⁇ 24 hrs or more.
• the water vapor permeability is preferably less than 100 g "m 2 ⁇ 24 hrs. 0 mmH is good is at 2 greater than or equal to zero.
• the temperature at which water vapor is actively released and the temperature at which heat retention is achieved can be adjusted according to the application according to the glass transition point of the polyurethane resin.
• the glass transition point of the polyurethane resin used in the present invention is 120 ° C to 20 ° C.
• the moisture-permeable waterproof fabric of the present invention having such a structure, exhibits excellent moisture permeability under a high-temperature and high-humidity environment, suppresses moisture permeability under a low-temperature environment, and has excellent heat retention. Therefore, it is possible to positively control the temperature and humidity environment in the manufacturing.
• a method for producing the moisture-permeable waterproof fabric of the present invention will be described.
• a solution of a polar organic solvent containing the above-mentioned polyurethane resin is applied to at least one surface of the fabric in an amount of preferably 3 to 50 g / m 2. Then, coagulate and remove the solvent, and dry. At this time, from the viewpoint of maintaining good texture, it is preferable that the applied amount of the polyurethane resin after drying is 3 to 10 g / m 2 .
• the polar organic solvent used as the solvent for the polyurethane resin is soluble in the resin, solidified and desolubilized. From the viewpoint of easiness of the medium, it is preferable that the selection is mainly made of a water-soluble polar organic solvent such as dimethylformamide (hereinafter referred to as DMF), dimethylacetamide, N-methylpyrrolidone. Further, an isocyanate-based cross-linking agent or a surfactant may be added to the resin solution.
• the isocyanate-based cross-linking agent forms a cross-linked structure in the film by heat treatment after film formation, thereby contributing to the strength and durability of the film. Coagulation and desolvation may be performed according to a known wet coagulation method.
• an aqueous solution or water of the above solvent is preferably used.
• the solidification temperature is preferably in the range of 5 to 50 ° C. from the viewpoint of adjusting the diameter of the microporous pores formed in the resin film to an appropriate range. It is preferable to use water for the desolvation, and the temperature for the desolvation is preferably selected in the range of 10 to 80 ° C.
• the desolvated fabric is then dried by an ordinary method, and the drying temperature is preferably selected in the range of 60 to 140 ° C.
• a water repellent treatment may be performed after drying to impart a durable water repellent.A known water repellent can be used for the water repellent treatment. You. Further, it is preferable to perform a finishing set in order to improve the quality of the fabric product. Before applying the resin, the fabric may be subjected to a water-repellent treatment or a calendar treatment.
• the resin film obtained by the wet method easily becomes microporous, and a moisture-permeable waterproof fabric having good moisture permeability can be obtained.
• a solution of a volatile organic solvent containing the above-mentioned polyurethane resin is applied onto release paper in an amount of preferably 50 to 200 g / m 2.
• an adhesive resin is applied on the obtained resin film, and if necessary, dried at 40 to 150 ° C., and then adhered to at least one side of the fabric, and then the release paper is released.
• the amount of the applied polyurethane resin after drying is preferably from 10 to 50 g / m 2 , and toluene and methylethylketone are used as volatile solvents. Tone, isopropyl alcohol, dimethylformamide and the like are preferably used.
• an ultraviolet absorber, an antioxidant, a foaming agent and the like may be added to the resin solution.
• an isocyanate-based cross-linking agent or a surfactant may be added to the resin solution.
• An isocyanate-based crosslinking agent forms a crosslinked structure in a film by heat treatment after film formation, thereby contributing to the strength and durability of the film.
• a resin film may be applied to the resin film surface of the moisture-permeable waterproof fabric obtained from a known urethane resin according to the present invention by a dry method.
• Waterproof fabrics obtained by this method shows the 1 0 0 0 0 mmH 2 0 or more water pressure resistance.
• the moisture-permeable waterproof fabric according to the present invention has a temperature-dependent moisture permeability.
• the movement of water vapor that is, the transfer of latent heat is suppressed to maintain the heat retaining property.
• the latent heat is released by passing water vapor through to prevent stuffiness and prevent temperature rise. Therefore, when the moisture-permeable waterproof fabric of the present invention is used in windbreakers, skiers, work clothes, shoes, etc., it has waterproof properties and does not warm up before or during exercise. Sometimes, it is rich in heat retention, has high water vapor permeability when the body warms up during or after exercise, and provides clothing that is comfortable, comfortable, and has a good texture.
• the present invention will be described more specifically based on examples.
• the moisture permeability and water pressure resistance respectively, JISL 1 0 9 9 A- 1 method and JISL 1 0 9 2 (water pressure resistance 2 0 0 0 mmH 2 0
• the following are the low water pressure method, more than that Is measured by the high water pressure method.
• Polyester ponge fabric (with both vertical and horizontal threads, 75D-72F, vertical density: 101 Zinch, horizontal density: 80 inches) and a fluorine-based water repellent, Asahigard AG7 A 10% aqueous solution of 10 was padded, dried, and cured.
• the polyol was dissolved in DMF at 50 ° C. with stirring, and then diisocyanate was charged and stirred for about 1 hour to obtain a prepolymer.
• a chain extender was added dropwise to cause a polymerization reaction to obtain a 25% by weight DMF solution of a polyurethane resin.
• MDI as polyisocyanate-Polyethylene glycol with a molecular weight of 2000 and polyethylene glycol adipate diol with a molecular weight of 1200 as a polyol, and ethylene glycol as a chain extender in molar ratio 3.4: 0.5: 0.5: 2.5.
• the glass transition point of the obtained polyurethane resin was 0.2 ° C., and the fraction of ethylene oxide in the polymer was 8.4 mol Z kg.
• Polyester ponge fabric (with warp yarn and weft yarn 75 D-72 F, yarn density: 101 zinch, weft density: 80 inch) and fluorine A 10% aqueous solution of water repellent Asahigard AG710 was padded, dried, and cured.
• the polymer was stirred and dissolved in DMF at 50 ° C., and then the diisocyanate was charged and stirred for about 1 hour to obtain a prepolymer.
• a chain extender was added dropwise to cause a polymerization reaction to obtain a 25% by weight DMF solution of a polyurethane resin.
• MDI as a diisocyanate
• 4-butanediol as a chain extender was mixed at a molar ratio of 1.2: 0.7: 0.2: 0.2.
• the glass transition point of the obtained polyurethane resin was 3.0 ° C., and the fraction of ethylene oxide in the polymer was 11.3 mol / kg.
• a fluorine-based water repellent for polyester ponge fabric 75 D-72 F with warp and weft yarns, warp density: 101 Zinch, weft density: 80 Zinch
• a 10% aqueous solution of AG710 was padded, dried and cured. 50 polyols. C was dissolved in DMF with stirring, and then diisocyanate was charged, followed by stirring for about 1 hour to obtain a prepolymer. Next, a chain extender was added dropwise to cause a polymerization reaction to obtain a 25% by weight DMF solution of a polyurethane resin.
• MDI as a diisocyanate
• the glass transition point of the obtained polyurethane resin was 18.5 ° C, and the fraction of ethylene oxide in the polymer was 7.4 mol / k.
• a resin solution obtained by adding 20 parts by weight of methylethyl ketone and 80 parts by weight of toluene to 100 parts by weight of this solution was applied on release paper in an amount of 80 g / m 2 , and 1 2 Dried at 0 ° C. Next, toluene was added to 100 parts by weight of an ether-based polyurethane resin as a binder resin.
• a resin solution obtained by adding 60 parts by weight and 10 parts by weight of an isocyanate-based cross-linking agent Rezamin NE (manufactured by Dainichi Seika Co., Ltd.) is applied on the obtained resin film, and is adhered to one surface of the woven fabric. I combined. After aging all day and night, the release paper was peeled off to obtain a laminated fabric. The application amount of the polyurethane resin was 15 g Zm 2 after drying. With respect to the obtained fabric, the moisture permeability, the water pressure resistance, and the ratio of the water vapor transmission rate between when the temperature was low and when it was high were measured. Table 1 shows the results.
• Polyester knitted fabric (30 d, 20 gauge tricot) is used as the fabric, MDI is used as the diisocyanate, and the molecular weight is 2000 as the polyol.
• Glycol and polytetramethylene glycol having a molecular weight of 2000, and ethylene glycol as a chain extender at a molar ratio of 3.30: 0.55: 0.45: 2.40, and others were used.
• a laminated fabric was obtained in the same manner as in Example 3. At this time, the polyurethane resin gas The Las transition point was 118 ° C, and the fraction of ethylene oxide in the polymer was 7.8 mol / kg. With respect to the obtained fabric, the moisture permeability, the water pressure resistance, and the ratio of the water vapor transmission rate between when the temperature was low and when it was high were measured. Table 1 shows the results.
• Example 4 The same cloth as in Example 4 was used as the cloth, and a mixed resin solution having the following composition was applied to one surface and solidified in an aqueous solution for 5 minutes. Thereafter, the solvent was removed with water at 25 ° C., and dried to obtain a fabric having a microporous film with an applied amount of 27 g Zm 2 .
• Example 4 a fabric having a microporous membrane and a nonporous membrane was obtained by the same resin and method as in Example 4. The resulting fabric was measured for moisture permeability, water pressure resistance, and the ratio of water vapor permeability at low and high temperatures. Table 1 shows the results.
• Example 2 was repeated except that the molar ratio of MDI, polyethylene glycol, polyethylene glycol adipate diol and 1,4-butanediol was 3.3: 0.3: 0.7: 2.4.
• a coating fabric was obtained in exactly the same manner.
• the glass transition point of the polyurethane resin was 0.8 ° C., and the ethylene oxide fraction in the polymer was 4.54 mol Z kg.
• the moisture permeability, the water pressure resistance, and the ratio of the water vapor transmission rate between when the temperature was low and when the temperature was high were measured. The results are shown in Table 1. Comparative Example 2
• a coating fabric was obtained in exactly the same manner as in Example 2 except that a resin having a glass transition point of 150 ° C. was used as the polyurethane resin. Get With respect to the obtained fabric, the moisture permeability, the water pressure resistance, and the ratio of the water vapor transmission rate between the low temperature and the high temperature were measured. The results are shown in Table 1.
• a coating fabric was obtained in the same manner as in Example 2 except that a resin having a glass transition point of 150 ° C. and a high moisture permeability was used as the polyurethane resin.
• the resulting fabric was measured for moisture permeability, water pressure resistance, and the ratio of water vapor permeability at low and high temperatures. Table 1 shows the results.
• a laminated fabric was obtained in the same manner as in Example 4, except that a resin having a glass transition point of 150 ° C was used as the polyurethane resin.
• the obtained fabric was measured for moisture permeability, water pressure resistance, and the ratio of the water vapor permeability at low and high temperatures. Table 1 shows the results.
• Example 1 0.2 8.4 944 11232 1200 156 225 1.44
• Example 2 3.0 11.3 1060 15432 1000 200 310 1.55
• Example 4 -18 7.8 624 8064 15000 106 162 1.53
• Example 5- 18 7.8 508 6900 25000 96 138 1.43
• Comparative Example 1 0.8 4.5 520 6552 550 88 131 1.50
• Comparative Example 2 -50 648 5300 2000 101 106 1.04

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• Chemical & Material Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Engineering & Computer Science (AREA)
• Textile Engineering (AREA)
• Dispersion Chemistry (AREA)
• Laminated Bodies (AREA)
• Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
• Synthetic Leather, Interior Materials Or Flexible Sheet Materials (AREA)
• Polyurethanes Or Polyureas (AREA)

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• 1993
  • 1993-06-18 DE DE69320774T patent/DE69320774T2/de not_active Expired - Fee Related
  • 1993-06-18 WO PCT/JP1993/000827 patent/WO1994000631A1/ja active IP Right Grant
  • 1993-06-18 KR KR1019940700485A patent/KR960004914B1/ko not_active Expired - Fee Related
  • 1993-06-18 EP EP93913547A patent/EP0603410B1/en not_active Expired - Lifetime
  • 1993-06-19 TW TW82104955A patent/TW242659B/zh not_active IP Right Cessation

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