EP0933467B1 - Wärmehaltendes, dampfdurchlässiges und wasserundurchlässiges Textilflächengebilde - Google Patents

Wärmehaltendes, dampfdurchlässiges und wasserundurchlässiges Textilflächengebilde Download PDF

Info

Publication number
EP0933467B1
EP0933467B1 EP19990101487 EP99101487A EP0933467B1 EP 0933467 B1 EP0933467 B1 EP 0933467B1 EP 19990101487 EP19990101487 EP 19990101487 EP 99101487 A EP99101487 A EP 99101487A EP 0933467 B1 EP0933467 B1 EP 0933467B1
Authority
EP
European Patent Office
Prior art keywords
moisture
fabric
permeable
absorbing
heat
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.)
Expired - Lifetime
Application number
EP19990101487
Other languages
English (en)
French (fr)
Other versions
EP0933467A3 (de
EP0933467A2 (de
Inventor
Hiroyoshi c/o Toyo Boseki K.K. Kaibe
Akira c/o Lab. of Toyo Boseki K. K. Nishimoto
Katsuki Toyo Boseki K. K. Takahashi
Shigeki c/o Lab. of Toyo Boseki K. K. Fukuoka
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Toyobo Co Ltd
Original Assignee
Toyobo Co Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Priority claimed from JP04767598A external-priority patent/JP3341984B2/ja
Priority claimed from JP10285198A external-priority patent/JP3341985B2/ja
Priority claimed from JP10301873A external-priority patent/JP2000129574A/ja
Priority claimed from JP10307246A external-priority patent/JP2000126566A/ja
Application filed by Toyobo Co Ltd filed Critical Toyobo Co Ltd
Publication of EP0933467A2 publication Critical patent/EP0933467A2/de
Publication of EP0933467A3 publication Critical patent/EP0933467A3/de
Application granted granted Critical
Publication of EP0933467B1 publication Critical patent/EP0933467B1/de
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06NWALL, 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
    • D06N3/00Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/0056Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the compounding ingredients of the macro-molecular coating
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06MTREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/21Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/227Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of hydrocarbons, or reaction products thereof, e.g. afterhalogenated or sulfochlorinated
    • D06M15/233Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of hydrocarbons, or reaction products thereof, e.g. afterhalogenated or sulfochlorinated aromatic, e.g. styrene
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06MTREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/21Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/31Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated nitriles
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06MTREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M23/00Treatment of fibres, threads, yarns, fabrics or fibrous goods made from such materials, characterised by the process
    • D06M23/08Processes in which the treating agent is applied in powder or granular form
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06MTREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2200/00Functionality of the treatment composition and/or properties imparted to the textile material
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06MTREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2200/00Functionality of the treatment composition and/or properties imparted to the textile material
    • D06M2200/10Repellency against liquids
    • D06M2200/12Hydrophobic properties

Definitions

  • the present invention relates to moisture-permeable, waterproof fabrics capable of generating heat by absorption of moisture, reducing the humidity within clothing and inhibiting moisture condensation, the fabrics being useful for raincoats, sportswears such as wears for mountaineering, athletics, skiing, snowboarding and golf, casual wears such as men's wears, female dresses and coats, outerwears, uniforms for working in refrigerators or cold storage warehouses and so on.
  • Textile fabric products which require heat-retaining property include, for example, clothes worn in winter such as suits and coats, clothes for protection against cold such as jumpers, winter sportswears such as ski wears, uniforms for working in refrigerators or cold storage warehouses and so on.
  • Various methods have been proposed to improve the heat-retaining property of clothes, as by increasing an air layer using bundles of finer fibers or by incorporating ceramics or metals into fibers to produce a far-infrared ray effect.
  • the proposed methods for improving the heat-retaining property of clothes include those in which ceramics or metals are incorporated into fibers for far-infrared ray radiations as disclosed in Japanese Unexamined Patent Publication No.105,107/1988 (a process for producing fiber products) and Japanese Unexamined Patent Publication No.331,584/1995 (mite-proof, far-infrared ray-irradiated fibers).
  • these methods have the drawbacks that the incorporation of ceramics or metals into base fibers lowers the strength of base fibers and colors them.
  • the proposed methods include those wherein a ceramic- or metal-containing resin is coated or laminated on fibers. Proposed are, for example, sheets of materials having excellent heat-retaining property as disclosed in Japanese Unexamined Patent Publication No.162,641/1985; coated fabrics as disclosed in Japanese Unexamined Patent Publication No.35,887/1988; and cloth or paper products coated with ceramics as disclosed in Japanese Unexamined Patent Publication No.183,579/1989. These methods assure heat-retaining property but fail to reduce the humidity within clothing and to inhibit moisture condensation due to the moisture-absorbing or releasing properties of the additive.
  • the proposals include waterproof sheets (Japanese Unexamined Patent Publications No.17,256/1981 and No.20,679/1981); moisture-absorbing and releasing, waterproof sheets (Japanese Unexamined Patent Publication No.52,675/1985); air-impermeable, moisture-absorbing and releasing, waterproof sheets (Japanese Unexamined Patent Publications No.110,440/1985 and No.126,386/1985); dewing-inhibitory, waterproof sheets (Japanese Unexamined Patent Publication No.77,530/1989); moisture-permeable, waterproof fabrics (Japanese Unexamined Patent Publication No.9,631/1995); and fabrics coated with a moisture-absorbing and releasing, waterproof layer (Japanese Unexamined Patent Publication No.97,970/1991).
  • the present inventors successfully developed moisture-permeable, waterproof fabrics by immobilizing said organic fine particles on an unprocessed (base fabric) using a moisture-permeable resin as an adhesive, said fabrics being capable of generating heat on absorption of such moisture as sweat exuded from the human body and capable of reducing the humidity within clothing and inhibiting dewing due to excellent moisture-absorbing and releasing property of the fine particles.
  • Preferred embodiments of the present invention are as follows.
  • unprocessed fabric refers to a base fabric to be used in producing the heat-retaining, moisture-permeable, waterproof fabric of the present invention.
  • materials of the base fabric useful in the present invention include synthetic fibers such as polyamide fibers, polyester fibers and polyacrylonitrile fibers, semi-synthetic fibers such as rayon and acetate, natural fibers such as cotton and wool. These fibers are used in any form such as woven fabric, knitted fabric or non-woven fabric.
  • the moisture-permeable, waterproof resins to be used in the present invention insofar as they have a moisture permeability of at least 30 g/m 2 ⁇ hr as measured according to JIS L 1099, A-1 method (calcium chloride method) when provided in the form of a 30 ⁇ m-thick film and insofar as they are usable in immobilizing highly moisture-absorbing and releasing organic fine particles on the base fabric.
  • Acrylic resins, polyurethane resins and silicone resins are preferred in view of the touch of the obtained fabric.
  • Useful resins are those having a moisture permeability of preferably at least 70 g/m 2 ⁇ hr, more preferably 100 to 300 g/m 2 ⁇ hr. When the resin has a moisture permeability of more than 300 g/m 2 ⁇ hr, heat is abruptly evolved and lasts only for a short time. However, such resin can be used if a short period heat is useful.
  • the duration of generated heat can be extended, for example, by forming on the foregoing resin layer an overcoating of a resin which is free of highly moisture-absorbing and releasing organic fine particles and which has a lower moisture permeability than the underlying resin layer.
  • the overcoating shows a moisture permeability of 10 to 70 g/m 2 ⁇ hr and has a thickness of 5 to 50 ⁇ m.
  • the moisture-permeable, waterproof resin and highly moisture-absorbing and releasing organic fine particles are fixed on the surface of the base fabric, whereby the fabric is rendered heat-retaining, moisture-permeable and waterproof.
  • the foregoing resin layer is preferably formed on at least one surface of the base fabric. In this case, preferably the resin layer has a thickness of 2 to 300 ⁇ m.
  • the fabric of the invention is required to achieve a difference of at least 3% between the moisture absorption ratios at 95% RH (A (95)) and at 20% RH (A (20)).
  • a preferred difference is about 5 to about 30%.
  • a difference of less than 3% results in insufficient moisture absorption and fails to produce the contemplated results of the present invention.
  • Highly moisture-absorbing and releasing, hygroscopically heat-generating organic fine particles to be used in the invention can be any of those which are highly hygroscopic and highly moisture-releasable and which can emit heat on absorption of moisture.
  • preferred organic fine particles are those having a high moisture absorption ratio of 40% or more at 65% RH and an initial moisture-absorbing rate of 0.8%/min or more. These organic fine particles show a high heat-generating rate and excellent property of evolving heat on absorption of moisture. More preferred organic fine particles are those having a moisture absorption ratio of at least 45% and an initial moisture-absorbing rate of about 1.0 to about 10%/min.
  • suitable organic fine particles are those having not only said hygroscopicity but a water-absorbing capacity ratio in the range of preferably from 0.4 : 1 to 10 : 1, more preferably from 0.6 : 1 to 4 : 1.
  • water-absorbing capacity ratio refers to a water-absorbing capacity ratio which is given by the following method. Pure water is added to absolutely dried organic fine particles, the blend of water and particles is left to stand for 24 hours, the superfluous water is removed by decantation, and a weight ratio of water in the particles : particles is calculated from the weight of the water-containing particles.
  • an initial moisture-releasing rate is preferably 0.8%/min or more, more preferably about 1.0 to about 5.0%/min, at 90% RH (20°C) to 40% RH (20°C) in view of the effects of reducing the humidity within clothing and preventing dewing by release of absorbed moisture.
  • initial moisture-absorbing rate refers to an initial moisture-absorbing rate which is given by the following method.
  • the organic fine particles are vacuum-dried at 70°C for 12 hours, a moisture absorption ratio is measured after standing for 10 minutes in an atmosphere of 20°C, 65% RH, and a ratio of increase in moisture absorption ratio per minute is calculated.
  • initial moisture-releasing rate refers to an initial moisture-releasing rate which is given by the following method.
  • the organic fine particles are left to stand at 20°C, 90% RH for 24 hours for adjustment of humidity, the particles are transferred to an atmosphere of 20°C, 40% RH, the moisture absorption ratio is measured after standing for 10 minutes and a ratio of decrease in moisture absorption ratio per minute is calculated.
  • Examples of useful highly moisture-absorbing and releasing, hygroscopically heat-generating organic fine particles to be used in the invention are acrylic metal-modified particles containing a metal salt of carboxyl group and having a crosslinked structure introduced by hydrazine treatment of an acrylic resin composed of at least 60% by weight, preferably about 85 to about 99% by weight, of acrylonitrile as a monomer, a nitrogen content being increased by 1.0 to 15.0% by weight, at least 1.0 mmol/g, preferably about 2.0 to 10.0 mmols/g, of remaining nitrile group being chemically converted to a metal salt of carboxyl group by hydrolysis.
  • Useful metals are alkali metals such as sodium and potassium and alkaline earth metals such as calcium.
  • Highly moisture-absorbing and releasing, hygroscopically heat-generating organic fine particles to be used in the invention are required to have an average particle size of 30 ⁇ m or less, preferably 10 ⁇ m or less, more preferably 5 ⁇ m or less, for the purposes of increasing the moisture-absorbing and releasing rate, preventing the removal of particles from the resin layer and giving a smooth touch to the fabric.
  • the fine particles need to have a maximum particle size of 50 ⁇ m or less, preferably 20 ⁇ m or less, more preferably 10 ⁇ m or less, for the same purposes.
  • the fine particles of less than 0.01 ⁇ m in average particle size are difficult to handle in drying and in adding a resin and hence are undesirable.
  • the amount of highly moisture-absorbing and releasing organic fine particles to be used in the invention is an important factor affecting the heat-retaining property.
  • the amount of the particles to be used is 1 to 100% by weight, preferably 10 to 50% by weight, more preferably 20 to 40% by weight, based on the weight of the fibers of the base fabric. If the amount of the fine particles to be used is less than 1% by weight, the fabric fails to produce the desired extents of the effects, namely generating heat on absorption of moisture, reducing the humidity within clothing and preventing dewing. On the other hand, if the amount exceeds 50% by weight, the film is impaired in appearance and is noticeably lowered in strength.
  • a great temperature difference is preferred.
  • a difference of at least 0.5°C is required between the surface temperature T (blank) of the base fabric (as measured after the base fabric is absolutely dried, adjusted to a temperature of 32°C in an absolute dry condition and held for 10 seconds in an environment of 70% RH, 32°C) and the surface temperature T (sample) of the resin layer on the fabric (as measured after the resin-coated fabric is subjected to the same procedure).
  • the temperature difference is preferably about 1.0 to about 10°C, more preferably about 1.5 to about 8.0°C. In the case of a temperature difference of less than 0.5°C, the fabric is not warm to the touch and the contemplated results of the invention can not be produced.
  • the humidity within clothing is preferably 70% or less, more preferably 30 to 65% as measured by the evaluation method to be described later, in view of comfortableness when touched.
  • the amount of dewing is preferably 23 g/m 2 or less, more preferably 20 g/m 2 or less as measured according to the evaluation method to be described later, in view of comfortableness when touched.
  • the moisture-permeable, waterproof resin and the highly moisture-absorbing and releasing organic fine particles can be applied to the base fabric by coating, laminating, dipping, exhausting or other methods. There is no limitation on application methods insofar as they assure the contemplated effects of generating heat on absorption of moisture, reducing the humidity within clothing and preventing dewing.
  • Modes of application to be conducted in the present invention include methods wherein the resin is applied to the fabric by dipping or exhausting, a film incapable of giving said effects is laminated on the resin coating surface of fabric to impart waterproofness, methods wherein a film incapable of giving said effects is laminated on the fabric using the resin as an adhesive, and methods wherein a resin of lower moisture permeability is applied as an undercoat or topcoat on or under a resin film capable of giving said effects in order to control the temperature elevation and heat generating time.
  • Either the so-called dry method or wet method can be used in forming a film by coating or laminating.
  • a water repellent treatment can be applied to said base fabric.
  • a resin layer capable of hygroscopically generating heat, reducing the humidity within clothing and inhibiting dewing is formed on the fabric as by coating or laminating
  • a water repellent treatment can be carried out to control the degree of penetration of a resin solution into the fabric, the resin solution being used as a coating fluid or as an adhesive in laminating.
  • Useful water repellents include, for example, fluorine-containing water repellents, paraffin-based water repellents and so on.
  • silicone-type water repellents are not suitable to use because they tend to cause peeling of film.
  • the water repellent treatment can be done after applying the resin to the base fabric. In this case, any of water repellents including fluorine-containing, paraffin-based and silicone-type water repellents can be used.
  • a sample (about 100 g) was dried by hot air at 105°C for 5 hours and then the weight (W 0 ) was measured. About 100 g of said sample was left to stand in a desiccator at 20% RH (20°C) for 24 hours and the weight of the sample (W 1 ) was measured, while about 100 g of said sample was left to stand in a desiccator at 95% RH (20°C) for 24 hours and the weight of the sample (W 2 ) was measured.
  • a (20) (W 1 -W 0 )/W 0 (%)
  • a (95) (W 2 -W 0 )/W 0 (%)
  • ⁇ A (%) A (95) - A (20)
  • thermoelectric thermometer was set on the second piece of the fabric to check the elevation of temperature for 30 minutes. Unit: °C.
  • a 20 ⁇ m-thick film was produced and the strength of the film was measured according to JIS L 1096, bursting strength, A method (Müllen method). Unit: kg.
  • a resin-coated fabric and a base fabric of the same material and the same weight as the resin-coated fabric were absolutely dried (drying conditions: 120°C, 3 hours) and introduced into a desiccator. Then the desiccator was placed in an environment at 32°C, 70% RH for 10 hours or longer to adjust the temperatures of the fabrics. After the fabrics were withdrawn from the desiccator, the surface temperatures of the fabrics were measured 10 seconds later using THERMO TRACER TH 3100 and DETECTOR UNIT TH 3100 (trade names, manufactured by NEC San-ei Instruments Ltd.).
  • ⁇ T T (sample) - T (blank)
  • T (sample) is the surface temperature of the fabric with the resin layer (as measured after the fabric is absolutely dried, adjusted to a temperature of 32°C in an absolute dry condition and held for 10 seconds in an environment of 70% RH, 32°C)
  • T (blank) is the surface temperature of the base fabric of the same material and the same weight (as measured after the base fabric is absolutely dried, adjusted to a temperature of 32°C in an absolute dry condition and held for 10 seconds in an environment of 70% RH, 32°C).
  • the humidity within clothing was measured using a device for simulation of microclimate within clothing which device is disclosed in Japanese Examined Patent Publication No.19098/1989.
  • the disclosed device comprises (I) a wind-tunnel section for control of external environment conditions inclusive of temperature, humidity and air current, (II) a section for reproducing the conditions of human body, and (III) a section comprising artificial skin and clothes for reproducing the microclimate within clothing.
  • the sample was absolutely dried under the same conditions as in measuring the temperature of heat generated by absorption of moisture (120°C, 3 hours), placed into a desiccator, adjusted to a specific temperature by standing in an environment at 32°C and 70% RH for 10 hours or longer, withdrawn from the desiccator, arranged to direct the resin-coated surface of the fabric toward the artificial human skin. Then the measurement of humidity within clothing was commenced by a temperature-humidity sensor.
  • the section for reproducing the microclimate within clothing was taken out, a moisture-impermeable film (Saran Wrap, trade name for product of Asahi Chemical Industry Co., Ltd.) was accommodated in a combination of the section for reproducing the conditions of human body and the section for reproducing the microclimate within clothing, followed by cease of sweating. Then the section for reproducing the microclimate within clothing was set again, followed by cease of sweating for 30 minutes, to complete the measurement.
  • the maximum humidity value was indicated as a representative value of measurements of humidity within clothing.
  • the sample was taken out immediately after measuring the microclimate within clothing. Thereafter water droplets were wiped off from the fabric surface directed to the artificial human skin. The amount of dewing was measured based on the change in the weight of fabric used for wiping. The amount of dewing was expressed in terms of weight per square meter (unit: g/m 2 ).
  • a fabric with a resin layer was cut to a piece, 20 cm in width and 30 cm in length, in an environment of 8°C, 55% RH. Then the piece of fabric was wound around a panelist's arm with the resin-coated surface of fabric turned inside. The end of the winding was attached to the underlying winding portion with a surgical tape. The panelist took exercise which consumed 150 kcal. (heart rate 127) as measured with an ergometer (TAKEI AERO FITNESSclair). The comfortableness of the fabric was evaluated in terms of warmness and dampness according to the following 5-grade ratings.
  • Hydrazine was added to the aqueous dispersion to give a concentration of 35% by weight in the bath.
  • the mixture was subjected to crosslinking procedure at 102°C for 2.5 hours.
  • NaOH was added to give a concentration of 10% by weight in the bath.
  • the mixture was hydrolyzed at 102°C for 5 hours, dialyzed in flowing water, desalted and dried, giving highly moisture-absorbing and releasing organic fine particles.
  • the fine particles thus obtained (hereinafter called “highly moisture-absorbing and releasing organic fine particles (P)”) had a nitrogen content increased by 3.3% by weight and an average particle size of 2 ⁇ m, contained 4.3 mmols/g of a salt of carboxyl group and showed a moisture absorption ratio of 45% at 65% RH (20°C).
  • Highly moisture-absorbing and releasing organic fine particles (P) showed moisture absorption ratios of 86% after standing for 24 hours in a desiccator at 90% RH (20°C); 68% after standing for 10 minutes in a desiccator at 40% RH (20°C); and 28% after standing for 1 hour in the same desiccator. These data confirmed that the particles (P) had the desired highly moisture-absorbing and releasing properties. The particles (P) showed a water-absorbing capacity ratio of 2.5.
  • the particles (Q) showed moisture absorption ratios of 46% at 65% RH, 80% at 90% RH and 33% after standing for 1 hour at 40% RH, and an initial moisture-absorbing rate of 0.8%/min.
  • the particles (Q) had a water-absorbing capacity ratio of 2.3.
  • the particles (R) showed moisture absorption ratios of 50% at 65% RH, 83% at 90% RH and 30% after standing for 1 hour at 40% RH, and an initial moisture-absorbing rate of 0.9%/min.
  • the particles (R) had a water-absorbing capacity ratio of 2.6.
  • the obtained base fabric was coated with a solution comprising the highly moisture-absorbing and releasing organic fine particles, resin, solvent and additives shown below in Tables 1-3 in the indicated amounts.
  • the amounts of particles and other materials were expressed in part by weight.
  • Hi-muren Y-237 is a trade name for a polyurethane resin manufactured by Dainichi Seika Color & Chemicals MGF. Co., Ltd.
  • Resamine X-100 is a trade name for a crosslinking agent (manufactured by Dainichi Seika Color & Chemicals MGF. Co., Ltd.) for polyurethane resins.
  • Paracron AM-200 is a trade name for an acrylic resin manufactured by Negami Kogyo Co., Ltd.
  • Panron LN is a trade name for a crosslinking agent (manufactured by Negami Kogyo Co., Ltd.) for acrylic resins.
  • Paracron PE-30 is a trade name for a silicone resin manufactured by Negami Kogyo Co., Ltd.
  • Catalyst C46 is a trade name for a catalyst (manufactured by Negami Kogyo Co., Ltd.) for silicone resins.
  • Ex.1 Ex.2 Comp. Ex.1 Hi-muren Y-237 100 100 100 Methyl ethyl ketone 20 20 20 20 Resamine X-100 2 2 2 Highly moisture-absorbing and releasing organic fine particles (P) 5 30 0
  • Ex.3 Ex.4 Comp. Ex.2 Paracron AM-200 100 100 100 Toluene 10 20 20 Panron LN 2 2 2 2 Highly moisture-absorbing and releasing organic fine particles (P) 5 30 0
  • Comp. Ex.3 Comp. Ex.4 Comp. Ex.5 Paracron PE-30 100 100 100 Catalyst C46 2 2 2 Ethyl acetate 20 20 20 20 Highly moisture-absorbing and releasing organic fine particles (P) 5 30 0
  • Solutions were prepared with concentrations in solvents adjusted to a viscosity of 10000 Pa (cps) (as measured with a B-type viscometer, rotor No.5, number of revolutions 20 rpm).
  • the fabrics were coated with the solutions using an applicator having a clearance of 50 ⁇ m. After coating, the coating layer was cured at 130°C for 1 minute.
  • Tables 4 and 5 show the results of evaluating the properties of the coated fabrics.
  • a coated fabric was produced by the same procedure as in Example 2 with the exception of using highly moisture-absorbing and releasing organic fine particles (Q) in place of the highly moisture-absorbing and releasing organic fine particles (P).
  • the obtained coated fabric showed a water pressure resistance of 0.8 kg/m 2 , a moisture permeability of 180 g/m 2 ⁇ hr, a heat-retaining property of 1.5°C, a film strength of 0.3 kg, a difference in hygroscopic degree ( ⁇ A) of 10.1% and a difference in temperature of heat generated by absorption of moisture ( ⁇ T) of 3.6°C.
  • Coated fabrics were produced in Examples 6-9 by the same procedure as in Examples 1 to 4, respectively with the exception of using highly moisture-absorbing and releasing organic fine particles (R) in place of the highly moisture-absorbing and releasing organic fine particles (P).
  • Coated fabrics were produced in Examples 10 to 13 in the same manner as in Examples 6 to 9, respectively with the exception of using an applicator having a clearance of 220 ⁇ m.
  • the properties of the obtained coated fabrics were evaluated with the results shown in Table 7.
  • Paracron SS-2500 (trade name for an acrylic resin manufactured by Negami Kogyo Co., Ltd., solid content 20% by weight, toluene used as a solvent).
  • Panron LN (trade name for a crosslinking agent manufactured by Negami Kogyo Co., Ltd. for acrylic resins).
  • Urethane resin A prepared by copolymerizing in the conventional manner polytetramethylene glycol (molecular weight 1000), polyethylene glycol (molecular weight 1000), neopentyl glycol and metaxylylene diisocyanate in a 70/30/16/63 weight ratio, solid content 25% by weight, methyl ethyl ketone used as a solvent, viscosity 50000 cps).
  • a solution was prepared as follows. Paracron SS-2500 (100 parts by weight) was uniformly mixed with 13.3 parts by weight of highly moisture-absorbing and releasing organic fine particles (P). The mixture was diluted with toluene to a viscosity of 10000 cps.
  • a moisture-permeable, waterproof fabric was produced by the same procedure as in Example 16 except that the amount of highly moisture-absorbing and releasing organic fine particles (P) was changed to 5 parts by weight.
  • the proportion of highly moisture-absorbing and releasing organic fine particles (P) in the resin layer on the fabric was 20% by weight (as calculated) based on the weight of the fibers.
  • a moisture-permeable, waterproof fabric was produced by the same procedure as in Example 16 with the exception of not using highly moisture-absorbing and releasing organic fine particles.
  • a solution was prepared as follows. Paracron SS-2500 (100 parts by weight) was uniformly mixed with 13.3 parts by weight of silica gel (silica gel blue manufactured by NAKAMURA CHEMICAL CO., LTD., medium-size particles, average particle size 2.2 ⁇ m, crushed to a maximum particle size of 9 ⁇ m). The mixture was diluted with toluene to a viscosity of 10000 cps.
  • Table 9 below shows the composition and the properties of the moisture-permeable, waterproof fabrics prepared in Examples 16 and 17 and Comparative Examples 6 and 7.
  • the resulting fabric showed a great difference in temperature of heat generated by absorption of moisture, a lower humidity within clothing, a reduced amount of dewing, an enhanced moisture permeability and excellent comfortableness as compared with a fabric free of such organic particles.
  • silica gel was added, the obtained fabric afforded good results in some properties but gave only slight comfortableness when touched. This disadvantage is presumably attributable to lower capabilities of silica gel (moisture content 30% at 65% RH, initial moisture-absorbing rate 0.6%/min, and initial moisture-releasing rate 0.5%/min) than highly moisture-absorbing and releasing organic fine particles.
  • a solution was prepared as follows. One hundred parts by weight of a stock solution of urethane resin A was uniformly mixed with 16.7 parts by weight of highly moisture-absorbing and releasing organic fine particles (P). The mixture was diluted with methyl ethyl ketone to a viscosity of 10000 cps.
  • the base fabric was coated with the solution by an applicator having a clearance of 35 ⁇ m.
  • the coating film was dried at 80°C for 3 minutes and cured at 130 °C for 3 minutes to produce a moisture-permeable, waterproof fabric.
  • the proportion of highly moisture-absorbing and releasing organic fine particles (P) in the resin layer on the fabric was 40% by weight based on the weight of the fibers.
  • a moisture-permeable, waterproof fabric was produced by the same procedure as in Example 18 except that the amount of highly moisture-absorbing and releasing organic fine particles (P) was changed to 6.3 parts by weight.
  • the proportion of highly moisture-absorbing and releasing organic fine particles (P) in the resin layer on the fabric was 20% by weight (as calculated) based on the weight of the fibers.
  • a moisture-permeable, waterproof fabric was produced by the same procedure as in Example 18 with the exception of not using highly moisture-absorbing and releasing organic fine particles.
  • a solution was prepared as follows. One hundred parts by weight of a stock solution of urethane resin A was uniformly mixed with 16.7 parts by weight of the silica gel used in Comparative Example 7. The mixture was diluted with methyl ethyl ketone to a viscosity of 10000 cps.
  • the fabric was coated with the solution by an applicator having a clearance of 35 ⁇ m.
  • the coating film was dried at 80°C for 3 minutes and cured at 130 °C for 3 minutes to produce a moisture-permeable, waterproof fabric.
  • the proportion of silica gel in the resin layer on the fabric was 40% by weight based on the weight of the fibers.
  • Table 10 below shows the composition and the properties of the moisture-permeable, waterproof fabrics prepared in Examples 18 and 19 and Comparative Examples 8 and 9.
  • a fabric to be treated was produced by weaving nylon filament yarns composed of 50 d/48 f at a pick spacing of 44 yarns/cm (112 yarns/inch) and an end spacing of 68 yarns/cm (175 yarns/inch) and dyeing the fabric with an acidic dye by a Jigger dyeing machine.
  • the dyed fabric was treated with the materials having the composition shown in Table 11 using a usual padding mangles at a mangle expression of 80% by a 1-dip 1-nip method, followed by drying at 100°C. Thereafter the fabric was heat-treated at 130°C for 5 minutes.
  • the amount of the materials is expressed in part by weight in Table 11.
  • the trade names indicate the following materials.
  • Elastron F-29 is a trade name for water-soluble polyurethane manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd. with a solid content of 30% by weight.
  • Catalyst 32 is a trade name for a catalyst manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.
  • Toresin FS-350 is a trade name for water-soluble nylon manufactured by Teikoku Chemical Industries Co., Ltd. with a solid content of 30% by weight.
  • AS-20 is a trade name for amino-modified silicone manufactured by Hiramatsu Yuka Kogyo Co., Ltd. with a solid content of 30% by weight.
  • Resins B, C and D and Catalysts B' and C' used in Examples 22 and 23 and Comparative Examples 11 and 12 to be described later refer to the following resins and catalysts:
  • 6-nylon fibers (2 denier and fiber length 38 mm) and polyester fibers (2 denier and fiber length 38 mm) were subjected to opening and fiber blending procedures (blending ratio 80/20) by opening machines.
  • a web was formed using cards and was laminated into cross layers. Thereafter the web was subjected to thermocompression bonding by calender rolls (200°C, linear pressure 80 kgf/cm 2 , velocity 30 m/min) to give a non-woven fabric weighing 26 g/m 2 and having a thickness of 2 mm and a lengthwise strength of 2.0 kgf/5 cm.
  • the non-woven fabric was treated with an aqueous dispersion of highly moisture-absorbing and releasing organic fine particles (P) (average particle size 2 ⁇ m), Resin B and Catalyst B', using usual padding mangles at a mangle expression of 80% by a 1-dip 1-nip method, followed by drying at 100°C for 3 minutes. Thereafter the fabric was heat-treated at 130°C for 5 minutes to give a processed fabric.
  • the amounts of the resin, catalyst and fine particles applied to the fabric were 8.0 parts by weight of Resin B, 0. 5 part by weight of Catalyst B' and 5 parts by weight of the fine particles, per 100 parts by weight of the processed fabric, all calculated as solids.
  • the obtained processed fabric achieved a remarkable degree of heat generation on absorption of moisture as compared with non-woven fabrics free of highly moisture-absorbing and releasing organic fine particles and prevented dewing without the undesired results such as reduction of strength nor removal of fine particles due to rubbing.
  • a processed fabric was produced in the same manner as in Example 22 with the exception of changing the amount of organic fine particles to 20 parts by weight.
  • Table 12 a highly moisture-absorbing and releasing, hygroscopically heat-generating non-woven fabric with enhanced hygroscopically heat-generating property was obtained by using an increased amount of fine particles.
  • a processed fabric was produced in the same manner as in Example 22 with the exception of not using the organic fine particles. As apparent from Table 12 below, neither hygroscopic heat generation nor dewing inhibition was not demonstrated by using only the resin and the catalyst.
  • a processed fabric was produced in the same manner as in Example 22 with the exception of changing the amount of organic fine particles to 0.5 part by weight. As seen from Table 12 below, neither hygroscopic heat generation nor dewing inhibition was not demonstrated when the fine particles were used only in a small amount of less than 1% by weight based on the weight of the fibers.
  • Table 12 below shows the composition of the fabrics and the properties thereof prepared in Examples 22 and 23 and Comparative Examples 11 and 12.
  • the non-woven fabric to be evaluated was placed in an atmosphere of 20°C and 65% RH for 24 hours to adjust the humidity. Then the fabric was laid as a cover over the upper opening of a 200 ml beaker containing 100 ml of hot water (50°C) in the atmosphere of the same temperature and the same humidity and was held in position with a rubber band for 1 hour. Then, after the fabric was displaced, its surface side facing the liquid surface was inspected to find out whether dew condensation occurred or not.
  • the moisture-permeable, waterproof fabric of the present invention assures retaining heat generated by absorption of moisture, reduction of humidity within clothing and dewing inhibition, because highly moisture-absorbing and releasing, hygroscopically heat-generating organic fine particles are immobilized on the fabric with a moisture-permeable resin, and the fine particles evolve heat on absorption of moisture without hindrance.

Landscapes

  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Laminated Bodies (AREA)

Claims (8)

  1. Wärmerückhaltendes, feuchtigkeitsdurchlässiges, wasserfestes Textilflächengebilde mit stark feuchtigkeitsabsorbierenden und -freisetzenden organischen Feinteilchen, die auf mindestens einer Oberfläche eines unbearbeiteten Textilflächengebildes (Basistextilflächengebilde) mit einem feuchtigkeitsdurchlässigen, wasserfesten Harz immobilisiert sind, wobei das Textilflächengebilde (verarbeitetes Textilflächengebilde) zum Erreichen eines Unterschieds in dem Hygroskopiegrad (ΔA), dargestellt durch die folgende Gleichung (1), und eines Unterschieds in der Temperatur von durch Absorption von Feuchtigkeit generierter Wärme (ΔT), dargestellt durch die folgende Gleichung (2): ΔA = A (95) - A (20) ≥ 3 (%) wobei A (95) ein Feuchtigkeitsabsorptionsverhältnis (%) des verarbeiteten Textilflächengebildes, gemessen nach Stehenlassen für 24 Stunden bei einer relativen Feuchtigkeit von 95% (20°C), darstellt,
    und
    A (20) ein Feuchtigkeitsabsorptionsverhältnis (%) des verarbeiteten Textilflächengebildes, gemessen nach Stehenlassen für 24 Stunden bei einer relativen Feuchtigkeit von 20% (20°C), darstellt und ΔT = T (Probe) - T (Blindwert) ≥ 0,5 (°C) wobei T (Probe) die Oberflächentemperatur des verarbeiteten Textilflächengebildes darstellt, die gemessen wird, nachdem das Textilflächengebilde absolut getrocknet ist, auf eine Temperatur von 32°C unter einer absolut trockenen Bedingung eingestellt ist und für 10 Sekunden unter einer Umgebung von 70% RH und 32°C gehalten wird, und T (Blindwert) die Oberflächentemperatur des unbearbeiteten Textilflächengebildes (Basistextilflächengebilde) darstellt, die gemessen wird, nachdem das Textilflächengebilde absolut getrocknet ist, auf eine Temperatur von 32°C unter einer absolut trockenen Bedingung eingestellt ist und für 10 Sekunden unter einer Umgebung von 70% RH und 32°C gehalten wird, befähigt ist, wobei die stark feuchtigkeitsabsorbierenden und -freisetzenden organischen Feinteilchen eine anfängliche Feuchtigkeitsabsorptionsrate von 0,8 %/min oder mehr bei 20°C und 65% RH zeigen, ein Verhältnis des Wasserabsorptionsvermögens in einem Bereich von 0,4:1 bis 10:1 aufweisen und eine durchschnittliche Teilchengröße von 0,01 µm bis 30 µm aufweisen und wobei die Menge der stark feuchtigkeitsabsorbierenden und -freisetzenden organischen Feinteilchen 1 bis 100 Gew.-%, bezogen auf die Fasern des Basistextilflächengebildes, beträgt.
  2. Wärmerückhaltendes, feuchtigkeitsdurchlässiges, wasserfestes Textilflächengebilde nach Anspruch 1, wobei der Unterschied in der Temperatur der durch Absorption von Feuchtigkeit generierten Wärme (ΔT) in einem Bereich von etwa 1,0 bis etwa 10,0°C liegt.
  3. Wärmerückhaltendes, feuchtigkeitsdurchlässiges, wasserfestes Textilflächengebilde nach Anspruch 2, wobei der Unterschied in der Temperatur der durch Absorption von Feuchtigkeit generierten Wärme (ΔT) in einem Bereich von etwa 1,5 bis etwa 8,0°C liegt.
  4. Wärmerückhaltendes, feuchtigkeitsdurchlässiges, wasserfestes Textilflächengebilde nach einem der Ansprüche 1 bis 3, wobei das feuchtigkeitsdurchlässige, wasserfeste Harz, das stark feuchtigkeitsabsorbierende und -freisetzende organische Feinteilchen enthält, in Form einer Schicht auf mindestens einer Oberfläche des Basistextilflächengebildes immobilisiert ist.
  5. Wärmerückhaltendes, feuchtigkeitsdurchlässiges, wasserfestes Textilflächengebilde nach einem der Ansprüche 1 bis 4, wobei die stark feuchtigkeitsabsorbierenden und -freisetzenden organischen Feinteilchen Feinteilchen aus einem Acrylharz sind, das aus mindestens 60 Gew.-% Acrylnitril als Monomer aufgebaut ist, wobei dem Acrylharz durch Hydrazinbehandlung eine vernetzte Struktur verliehen wird und der Stickstoffgehalt um 1,0 bis 15,0 Gew.-% erhöht wird, wobei mindestens 1,0 mmol/g zurückbleibende Nitrilgruppen chemisch durch Hydrolyse in ein Salz einer Carboxylgruppe umgewandelt sind.
  6. Wärmerückhaltendes, feuchtigkeitsdurchlässiges, wasserfestes Textilflächengebilde nach einem der Ansprüche 1 bis 5, wobei das feuchtigkeitsdurchlässige, wasserfeste Harz eine Feuchtigkeitsdurchlässigkeit von mindestens 30 g/m2·h, gemessen in Form eines 30 µm dicken Films, aufweist.
  7. Wärmerückhaltendes, feuchtigkeitsdurchlässiges, wasserfestes Textilflächengebilde nach Anspruch 6, wobei das feuchtigkeitsdurchlässige, wasserfeste Harz eine Feuchtigkeitsdurchlässigkeit von mindestens 70 g/m2·h aufweist.
  8. Wärmerückhaltendes, feuchtigkeitsdurchlässiges, wasserfestes Textilflächengebilde nach einem der Ansprüche 4 bis 7, wobei eine Schicht aus einem Harz mit einer Dicke von 5 bis 50 µm und einer Feuchtigkeitsdurchlässigkeit von 10 bis 70 g/m2·h auf der Schicht des feuchtigkeitsdurchlässigen, wasserfesten Harzes, das stark feuchtigkeitsabsorbierende und -freisetzende organische Feinteilchen enthält, gebildet ist.
EP19990101487 1998-01-28 1999-01-27 Wärmehaltendes, dampfdurchlässiges und wasserundurchlässiges Textilflächengebilde Expired - Lifetime EP0933467B1 (de)

Applications Claiming Priority (10)

Application Number Priority Date Filing Date Title
JP1582798 1998-01-28
JP1582798 1998-01-28
JP4767598 1998-02-27
JP04767598A JP3341984B2 (ja) 1998-02-27 1998-02-27 保温性発熱布帛
JP10285198A JP3341985B2 (ja) 1998-01-28 1998-04-14 保温性透湿防水布帛
JP10285198 1998-04-14
JP10301873A JP2000129574A (ja) 1998-10-23 1998-10-23 高吸放湿吸湿発熱性不織布
JP30187398 1998-10-23
JP30724698 1998-10-28
JP10307246A JP2000126566A (ja) 1998-10-28 1998-10-28 抗血栓性の向上した血液浄化膜

Publications (3)

Publication Number Publication Date
EP0933467A2 EP0933467A2 (de) 1999-08-04
EP0933467A3 EP0933467A3 (de) 2000-11-29
EP0933467B1 true EP0933467B1 (de) 2004-08-25

Family

ID=27519750

Family Applications (1)

Application Number Title Priority Date Filing Date
EP19990101487 Expired - Lifetime EP0933467B1 (de) 1998-01-28 1999-01-27 Wärmehaltendes, dampfdurchlässiges und wasserundurchlässiges Textilflächengebilde

Country Status (2)

Country Link
EP (1) EP0933467B1 (de)
DE (1) DE69919605T2 (de)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6774065B2 (en) 2000-08-09 2004-08-10 Toray Industries, Inc. Waterproof-finished fabric and waterproof clothing
TWI229037B (en) * 2000-09-29 2005-03-11 Toray Industries Fiber structure of heat retaining property
JP4516204B2 (ja) * 2000-11-27 2010-08-04 東洋紡績株式会社 透湿性防水布帛
JP4375397B2 (ja) 2004-03-03 2009-12-02 日本エクスラン工業株式会社 吸放湿紙およびその製造法
WO2013157085A1 (ja) * 2012-04-18 2013-10-24 株式会社オーシンエムエルピー 多層シート及びそれを備える保温用構造物

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS60126386A (ja) * 1983-12-12 1985-07-05 Hiraoka & Co Ltd 非通気性吸放湿性防水シ−ト
JP2580724B2 (ja) * 1988-06-28 1997-02-12 日本エクスラン工業株式会社 難燃性繊維の製造法
JPH0759762B2 (ja) * 1993-04-05 1995-06-28 美津濃株式会社 吸放湿吸水発熱性保温品
JP2989765B2 (ja) * 1995-10-16 1999-12-13 東洋紡績株式会社 保温性、吸放湿吸水発熱性を有する複合材の製造方法
CA2300866C (en) * 1998-06-24 2005-08-16 Mizuno Corporation Moisture absorbing/releasing and heat generating inner cloth and method of producing it and moisture absorbing/releasing, heat generating and heat-retaining articles

Also Published As

Publication number Publication date
DE69919605T2 (de) 2005-07-14
DE69919605D1 (de) 2004-09-30
EP0933467A3 (de) 2000-11-29
EP0933467A2 (de) 1999-08-04

Similar Documents

Publication Publication Date Title
US6046119A (en) Heat-retaining, moisture-permeable, waterproof fabrics
Lomax The design of waterproof, water vapour-permeable fabrics
US4822667A (en) Woven medical fabric
US5024851A (en) Process for preparing a woven medical fabric
US6774065B2 (en) Waterproof-finished fabric and waterproof clothing
CA2602258A1 (en) Fiber treatment agent, fiber treated with the fiber treatment agent, fiber fabric, laminate body and fiber treatment method
EP3738652A1 (de) Wasserbeständige schutzkleidung
EP1156152A1 (de) Feuchtigkeitabsorbierendes und -abgebendes Tuch und Verfahren zu seiner Herstellung
EP0933467B1 (de) Wärmehaltendes, dampfdurchlässiges und wasserundurchlässiges Textilflächengebilde
JP4508669B2 (ja) 透湿防水保温性布帛およびその製造方法
JP3724351B2 (ja) 防水衣料
KR100556062B1 (ko) 보온성 투습방수직물
JP2002180308A (ja) 保温衣料
JP2000129574A (ja) 高吸放湿吸湿発熱性不織布
JP3342002B2 (ja) 吸湿発熱、衣服内湿度低減及び結露防止性を有する透湿防水布帛
JPH0754277A (ja) 透湿防水性コーティング布帛の製造方法
JPH06316871A (ja) 透湿性防水布帛およびその製造方法
JP3736667B2 (ja) 透湿防水布帛
JP2002061077A (ja) 防水加工布帛およびその製造方法
JP3273144B2 (ja) 透湿性防水布帛
JP2845517B2 (ja) 透湿性防水布帛
JP2001131875A (ja) 透湿防水布帛
JPH04146265A (ja) 清涼感に優れた繊維構造物及びその製造方法
JP2004068212A (ja) 透湿防水布帛
JPS59137577A (ja) 保温性の優れた防水透湿布帛およびその製造方法

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Kind code of ref document: A2

Designated state(s): DE IT

AX Request for extension of the european patent

Free format text: AL;LT;LV;MK;RO;SI

PUAL Search report despatched

Free format text: ORIGINAL CODE: 0009013

RIC1 Information provided on ipc code assigned before grant

Free format text: 7D 06N 7/00 A, 7D 06N 3/00 B, 7D 06M 23/08 B, 7D 06M 15/356 B, 7D 06M 15/31 B

AK Designated contracting states

Kind code of ref document: A3

Designated state(s): AT BE CH CY DE DK ES FI FR GB GR IE IT LI LU MC NL PT SE

AX Request for extension of the european patent

Free format text: AL;LT;LV;MK;RO;SI

17P Request for examination filed

Effective date: 20010426

AKX Designation fees paid

Free format text: DE IT

17Q First examination report despatched

Effective date: 20030912

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): DE IT

REF Corresponds to:

Ref document number: 69919605

Country of ref document: DE

Date of ref document: 20040930

Kind code of ref document: P

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed

Effective date: 20050526

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20070129

Year of fee payment: 9

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: IT

Payment date: 20070509

Year of fee payment: 9

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20080801

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20080127