EP2473668B1 - Textiles flächengebilde aus aramidfasern und dessen verwendung - Google Patents

Textiles flächengebilde aus aramidfasern und dessen verwendung Download PDF

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Publication number
EP2473668B1
EP2473668B1 EP20100745650 EP10745650A EP2473668B1 EP 2473668 B1 EP2473668 B1 EP 2473668B1 EP 20100745650 EP20100745650 EP 20100745650 EP 10745650 A EP10745650 A EP 10745650A EP 2473668 B1 EP2473668 B1 EP 2473668B1
Authority
EP
European Patent Office
Prior art keywords
thread group
threads
fabric
layer
textile 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.)
Active
Application number
EP20100745650
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German (de)
English (en)
French (fr)
Other versions
EP2473668A1 (de
Inventor
Rüdiger Hartert
Peter Gerard Akker
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.)
Teijin Aramid GmbH
Original Assignee
Teijin Aramid GmbH
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
Application filed by Teijin Aramid GmbH filed Critical Teijin Aramid GmbH
Priority to EP20100745650 priority Critical patent/EP2473668B1/de
Publication of EP2473668A1 publication Critical patent/EP2473668A1/de
Application granted granted Critical
Publication of EP2473668B1 publication Critical patent/EP2473668B1/de
Active legal-status Critical Current
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Classifications

    • 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
    • D06M15/37Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/507Polyesters
    • D06M15/513Polycarbonates
    • DTEXTILES; PAPER
    • D01NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01FCHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F11/00Chemical after-treatment of artificial filaments or the like during manufacture
    • D01F11/04Chemical after-treatment of artificial filaments or the like during manufacture of synthetic polymers
    • D01F11/08Chemical after-treatment of artificial filaments or the like during manufacture of synthetic polymers of macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • DTEXTILES; PAPER
    • D01NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01FCHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/58Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products
    • D01F6/60Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polyamides
    • D01F6/605Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polyamides from aromatic polyamides
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F41WEAPONS
    • F41HARMOUR; ARMOURED TURRETS; ARMOURED OR ARMED VEHICLES; MEANS OF ATTACK OR DEFENCE, e.g. CAMOUFLAGE, IN GENERAL
    • F41H1/00Personal protection gear
    • F41H1/02Armoured or projectile- or missile-resistant garments; Composite protection fabrics
    • 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
    • D06M2101/00Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
    • D06M2101/16Synthetic fibres, other than mineral fibres
    • D06M2101/30Synthetic polymers consisting of macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M2101/34Polyamides
    • D06M2101/36Aromatic polyamides
    • DTEXTILES; PAPER
    • D10INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10BINDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2331/00Fibres made from polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polycondensation products
    • D10B2331/02Fibres made from polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polycondensation products polyamides
    • D10B2331/021Fibres made from polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polycondensation products polyamides aromatic polyamides, e.g. aramides
    • DTEXTILES; PAPER
    • D10INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10BINDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2401/00Physical properties
    • D10B2401/06Load-responsive characteristics
    • D10B2401/063Load-responsive characteristics high strength
    • DTEXTILES; PAPER
    • D10INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10BINDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2501/00Wearing apparel
    • D10B2501/04Outerwear; Protective garments
    • DTEXTILES; PAPER
    • D10INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10BINDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2507/00Sport; Military
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T442/00Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
    • Y10T442/20Coated or impregnated woven, knit, or nonwoven fabric which is not [a] associated with another preformed layer or fiber layer or, [b] with respect to woven and knit, characterized, respectively, by a particular or differential weave or knit, wherein the coating or impregnation is neither a foamed material nor a free metal or alloy layer
    • Y10T442/2861Coated or impregnated synthetic organic fiber fabric

Definitions

  • the invention relates to a textile fabric of aramid fibers and its use.
  • Textile fabrics of aramid fibers and their use for the production of eg antiballistically active textile fabrics are known. These fabrics typically contain aramid fibers which have been provided with equipment comprising a polyglycol ester of oleic acid during their manufacture. Such equipment is available under the designation Leomin OR from Clariant, DE. US 4,652,488 describes the equipment of aramid fibers with Leomin OR.
  • step 15) indicates that the residual content of the equipment is> 0.1% by weight, at least some of the steps 1) to 15) must be repeated until the permitted residual content of equipment of ⁇ 0.1% by weight .-% is achieved.
  • the present invention has the object, either the washing and masking process described above to provide a suitable for the application of a water repellent agent textile fabric of aramid fibers either completely redundant or at least significantly reduce the process cost.
  • a textile fabric made of aramid fibers which are equipped with a lubricant, wherein the lubricant comprises a carbonic acid polyester.
  • the textile fabric according to the invention can be rendered water-repellent directly, ie omitting the above-described 25-stage washing and masking process, and yet shows similarly good v 50 values as in the dry and wet condition in the case of ball and blade bombardment Aramid fibers with a polyglycol ester of oleic acid, which at the outset have yet to undergo the previously described washing and masking steps before its water-repellent finish.
  • the textile fabric according to the invention which is washed as described in the initially described process with steps 1) to 15), but in step 10) only 6 passages are carried out and in step 14) the fabric is sprayed with water only and not is omitted, and the masking steps 16) to 24) are omitted, even a v 50 value, which is higher than the v 50 value of a textile fabric with aramid fibers with a polyglycol ester of oleic acid comprising equipment, the before its water-repellent finish, all of the above-described 25 wash and mask steps must be completed.
  • textile fabrics of aramid fibers means that the textile fabric according to the invention consists of at least 80% by weight and preferably at least 95% by weight of aramid fibers.
  • the textile fabric according to the invention consists entirely of aramid fibers which are provided with a finishing agent, wherein the finishing agent comprises a carbonic acid polyester.
  • carbonic acid polyester means a polymer which is prepared by polycondensation of a carbonic acid ester or carbonic acid dichloride with one or more diols, wherein one or both chain ends of the carbonic acid polyester consist of a hydroxyl group or wherein one or both of the chain ends of the Carbonic acid polyester consist of an alkyl radical of a monovalent alcohol.
  • the carbonic acid ester used for the polycondensation is a dialkyl carbonate.
  • the diol used for the polycondensation may be an aliphatic diol or a polyalkylene glycol.
  • the carbonic acid polyester of the structural formula (I), its preferred embodiments and methods of preparation are in US 5,569,408 described.
  • the finishing agent used to finish the aramid fibers comprising the fabric of the present invention may consist of 100% of a carbonic acid polyester, which is preferably a carbonic acid polyester of structural formula (I).
  • the carbonic acid polyester preferably the carbonic acid polyester of the structural formula (I), as an aqueous solution or as a solution or emulsion in an organic solvent, e.g. in ethanol.
  • the finishing agent consists of a carbonic acid polyester of the formula (I), an alkylpolyglycol ether, a potassium alkyl phosphate and an ethyoxylated and / or propoxylated fatty alcohol, the substances mentioned being formulated in water.
  • a finish is available from Bozetto (Italy) under the brand Estesol NC 91.
  • the finishing agent consists of a carbonic acid polyester of the formula (I), an alkylpolyglycol ether, a potassium alkyl phosphate, an ethyoxylated alcohol and a polyglycol ester, the substances mentioned being formulated in water.
  • Such a finish is also available from Bozetto (Italy) under the brand Estesol CB 95.
  • the aramid fibers finished with the finishing agent have from 0.1 to 1.5% by weight, particularly preferably from 0.2 to 1.0% by weight, of avivage solids, based on their weight is meant by the sum of the solids of the carbonic acid polyester, preferably the carbonic acid polyester of the structural formula (I), and optionally the Alkylpolyglykolethers, the potassium alkyl phosphate, the ethoxylated and / or propoxylated fatty alcohol, the ethoxylated Alcohol and the polyglycol ester yields.
  • the carbonic acid polyester preferably the carbonic acid polyester of the structural formula (I)
  • comprehensive finishing on the aramid fibers each method is suitable, whereby the desired amount of finishing agent can be applied to the aramid fibers.
  • the finish comprising the carbonic acid polyester may be applied during the manufacturing process of the aramid fibers after washing and before drying with a nozzle or with an applicator or with a kiss roll, after which the aramid fibers are dried and be wound up.
  • Applying a kiss roll means that a rotating roll is partially immersed in a bath in which the softening comprising the carbonic acid polyester, e.g. as an aqueous solution.
  • a film is formed from the finishing agent comprising the carbonic acid polyester.
  • the aramid fibers are brought into contact with the film and thereby scavenged.
  • finishing comprising the carbonic acid polyester, preferably the carbonic acid polyester of the structural formula (I), in a process downstream of the aramid fiber production. This can be done e.g. unwind the fiber from the roll and bring it into contact with the lubricant, the finish being free of water and / or organic solvent and present as an oil or melt.
  • the textile fabric according to the invention can in principle be any type of fabric which can be produced from aramid fibers.
  • the textile fabric according to the invention is a woven, knitted or knitted fabric or a uniaxial or multiaxial fabric.
  • the term fabric encompasses all types of bonding, e.g. Plain weave, satin weave, Panama weave, twill weave and the like.
  • the fabric has plain weave.
  • the threads of each of the two fabric layers of the fabric double layer are joined together, for example by sewing or preferably by means of an adhesive material.
  • the adhesive material may be an adhesive.
  • the adhesive material may also be an adhesive layer provided between the two fabric layers of the fabric double layer.
  • adhesive materials thermoplastic or elastomeric or thermosetting materials can be used.
  • a material may be used which melts under pressure and / or heating, whereby the threads of the first thread group or the second thread group with the threads of the second thread group or the first thread group and optionally also the two fabric layers are joined together.
  • Thermoplastic materials useful as adhesive materials include polyolefins such as polyethylene and polypropylene, polyamides, polyesters, or blends of these materials.
  • Elastomeric materials useful as adhesive materials include Kraton® , rubber, silicone, and the like.
  • the thermosetting materials employable as adhesive materials are epoxy resins, polyester resins, phenolic resins, vinyl ester resins, and the like.
  • the fabric is a double layer of a fabric
  • at least one of the outer surfaces of the double layer with a Provided protective layer.
  • the protective layer may consist of a thermoplastic, a thermosetting or an elastomeric material or a mixture of these materials. The protective layer is applied to protect the fabric from damage caused by excessive scrubbing and to further improve the ballistic properties.
  • the textile fabric according to the invention is a double layer of a fabric
  • the two layers of the double layer are not crosswise to one another and are optionally connected to one another.
  • tissue encompasses all types of binding, such as e.g. Plain weave, satin weave, Panama weave, twill weave and the like.
  • the fabrics have plain weave.
  • the textile fabric according to the invention comprises aramid fibers.
  • aramid fibers preferably means filament yarns consisting of aramids, i. are prepared from aromatic polyamides wherein at least 85% of the amide (-CO-NH-) bonds are bonded directly to two aromatic rings.
  • aromatic polyamides for the present invention are p-aramids, especially poly-p-phenylene terephthalamide, a homopolymer resulting from the mol: mol polymerization of p-phenylenediamine and terephthalic acid dichloride. Therefore, in a preferred embodiment, the aramid fibers comprising the fabric according to the invention are p-aramid fibers, in particular poly-p-phenylene terephthalamide fibers and more preferably poly-p-phenylene terephthalamide filament yarns available under the name Twaron from Teijin Aramid GmbH (DE).
  • DE Teijin Aramid GmbH
  • aromatic copolymers in which para-phenylenediamine and / or terephthalic acid partially or completely substituted by other aromatic diamines and / or dicarboxylic acid chlorides.
  • the textile fabric of the present invention allows drastic simplification for providing a water-repellent finished fabric of aramid fibers. This advantage is correspondingly noticeable when the textile fabric according to the invention is used to produce a penetration-inhibiting article. Therefore, the use of the textile fabric according to the invention for the production of a penetration-inhibiting article is also part of the present invention.
  • At least one textile fabric according to the invention is used.
  • a plurality of textile fabrics according to the invention are used, wherein the person skilled in the art can determine the number of textile fabrics according to the invention to be used according to the intended penetration-inhibiting protective effect.
  • the textile fabric according to the invention is preferably used as a fabric, wherein at least one fabric is used. If multiple tissues are used, the tissues are stacked in a package. In the package, the individual webs can be unconnected to one another or preferably by sewing or by another suitable joining technique, such as sewing. by partial bonding, be connected to each other.
  • the textile fabric according to the invention is preferably used as a fabric double layer, wherein at least one fabric double layer is used becomes. If multiple tissue double layers are used, the tissue double layers are stacked in a package. However, the individual fabric double layers may be bonded together by stitching or with an adhesive layer, the adhesive layer preferably having a thickness of between 4 and 36 ⁇ m and more preferably a thickness of between 8 and 20 ⁇ m.
  • the package may consist of a succession of fabrics and fabric double layers according to the invention.
  • the tissues (G) and tissue double layers (D) according to the invention can follow one another alternately, ie in the sequence (G / D) n or preferably in blocks, ie for example in the sequence (G g / D d ) m .
  • n is the number of (G / D) pairs in the packet
  • m is the number of (G g / D d ) pairs in the packet
  • g is the number of tissues in tissue block G
  • d is the number of tissue bilayers in the tissue Double layer block D.
  • the penetration-inhibiting softballistic article is an anti-splintering mat, a bullet-proof vest, a splinter-proof vest, a stab-resistant vest or a combination of at least two of said articles.
  • a poly-p-phenylene terephthalamide filament yarn (Twaron Type 2040, 930dtex f1000 t0) is provided in its manufacturing process after washing and before drying with Leomin OR (Clariant, DE).
  • the dried fiber contains 0.6 to 0.8 wt .-% Leomin OR solid.
  • the yarn resulting from a) is processed into a web with L 1/1 binding at 10.5 threads per cm in warp and weft and with a basis weight of 200 g / m 2 .
  • the tissue resulting after step 25) of c) is passed through a temperature-controlled bath consisting of water and based on the water of 60 g / l Oleophobol SL, 30 g / l Oleophobol SM and 10 g / l Phobol XAN (all from Huntsman, DE). Thereafter, the fabric is squeezed, dried at 120 ° C and heat treated at a temperature of 190 ° C for 50 seconds.
  • the 22 layers of the resulting d) tissue are piled into a package.
  • the package is fired with ammunition type bullets 9mm DM 41 and the v 50 value determined.
  • the v 50 value of the dry package is 470 ⁇ 7 m / s (see table).
  • v 50 value of the package is 484 ⁇ 6 in the dry state and 466 ⁇ 8 m / s in the wet state (see table).
  • a poly-p-phenylene terephthalamide filament yarn (Twaron Type 2040, 930 dtex, f1000 t0) is equipped in its production process after washing and before drying with Estesol NC 91 from Bozetto (Italy).
  • the dried fiber contains 0.26% by weight of Estesol NC 91 solid.
  • the yarn resulting from a) is processed into a web with L 1/1 binding at 10.5 threads per cm in warp and weft and with a basis weight of 200 g / m 2 .
  • the tissue resulting from b) is passed through a temperature-controlled bath consisting of water and, based on the water, 60 g / l oleophobol SL, 30 g / l oleophobol SM and 10 g / l phobol XAN (all from Huntsman DE). Thereafter, the fabric is squeezed, dried at 120 ° C and heat treated at a temperature of 190 ° C for 50 seconds.
  • the 22 layers of the resulting d) tissue are piled into a package.
  • the package is fired with ammunition type bullets 9mm DM 41 and the v 50 value determined.
  • the v 50 value of the dry package is 475 ⁇ 8 m / s (see table).
  • Another 14 layers of the resulting tissue from d) are piled into a package.
  • the package will be fired with splitter type 1.1 FSP splinters and the v 50 value determined.
  • the v 50 value of the package is 493 ⁇ 13 in the dry state and 472 ⁇ 14 m / s in the wet state (see table).
  • a poly-p-phenylene terephthalamide filament yarn (Twaron Type 2040, 930 dtex, f1000 t0) is equipped in its production process after washing and before drying with Estesol NC 91 from Bozetto (Italy).
  • the dried fiber contains 0.26% by weight of Estesol NC 91 solid.
  • the yarn resulting from a) is processed into a fabric with L 1/1 binding, with 10.5 threads per cm in warp and weft and with a basis weight of 200 g / m 2 .
  • the tissue resulting from b) is prewashed as in the comparative example in steps 1) to 6) and washed in steps 7) to 11), but with the difference that in step 10) instead of 10 passages only 6 passages are carried out, which clearly shows less time, water and energy is consumed than in the comparative example.
  • the fabric passes through steps 12) -15), but with the difference that in step 14) the fabric is not rinsed but merely sprayed with water, which further reduces the water consumption in comparison with the comparative example.
  • the fabric is not masked but dried with omission of steps 16) -24) as in step 25) of the comparative example.
  • the tissue resulting from c) is passed through a room temperature-controlled bath consisting of water and based on the water of 60 g / l Oleophobol SL, 30 g / l Oleophobol SM and 10 g / l Phobol XAN (all from Huntsman DE). Thereafter, the fabric is squeezed, dried at 120 ° C and heat treated at a temperature of 190 ° C for 50 seconds.
  • the 22 layers of the resulting d) tissue are piled into a package.
  • the package is fired with ammunition type bullets 9mm DM 41 and the v 50 value determined.
  • the v 50 value of the dry package is 463 ⁇ 6 m / s (see table).
  • Another 14 layers of the resulting tissue from d) are piled into a package.
  • the package will be fired with splitter type 1.1 FSP splinters and the v 50 value determined.
  • the v 50 value of the package is 495 ⁇ 12 in the dry state and 490 ⁇ 8 m / s in the wet state (see table).

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Textile Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • General Engineering & Computer Science (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Woven Fabrics (AREA)
  • Professional, Industrial, Or Sporting Protective Garments (AREA)
  • Laminated Bodies (AREA)
EP20100745650 2009-09-03 2010-08-27 Textiles flächengebilde aus aramidfasern und dessen verwendung Active EP2473668B1 (de)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP20100745650 EP2473668B1 (de) 2009-09-03 2010-08-27 Textiles flächengebilde aus aramidfasern und dessen verwendung

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
EP09169383 2009-09-03
PCT/EP2010/062522 WO2011026782A1 (de) 2009-09-03 2010-08-27 Textiles flächengebilde aus aramidfasern und dessen verwendung
EP20100745650 EP2473668B1 (de) 2009-09-03 2010-08-27 Textiles flächengebilde aus aramidfasern und dessen verwendung

Publications (2)

Publication Number Publication Date
EP2473668A1 EP2473668A1 (de) 2012-07-11
EP2473668B1 true EP2473668B1 (de) 2013-07-31

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Family Applications (1)

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EP20100745650 Active EP2473668B1 (de) 2009-09-03 2010-08-27 Textiles flächengebilde aus aramidfasern und dessen verwendung

Country Status (8)

Country Link
US (2) US9834883B2 (https=)
EP (1) EP2473668B1 (https=)
JP (1) JP5547811B2 (https=)
KR (2) KR101763125B1 (https=)
CN (1) CN102597361B (https=)
IL (1) IL218416A0 (https=)
RU (1) RU2533134C2 (https=)
WO (1) WO2011026782A1 (https=)

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CN105768260A (zh) * 2014-12-23 2016-07-20 江苏金阳羽绒制品有限公司 防水羽绒服

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CN111691065B (zh) * 2020-06-18 2021-11-02 军事科学院系统工程研究院军需工程技术研究所 一种拒水保暖絮片及其制备方法

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Publication number Publication date
WO2011026782A1 (de) 2011-03-10
US20180044848A1 (en) 2018-02-15
JP5547811B2 (ja) 2014-07-16
KR101763125B1 (ko) 2017-07-31
RU2012112809A (ru) 2013-10-10
US9834883B2 (en) 2017-12-05
JP2013503982A (ja) 2013-02-04
US20120159698A1 (en) 2012-06-28
KR20170089954A (ko) 2017-08-04
CN102597361A (zh) 2012-07-18
EP2473668A1 (de) 2012-07-11
KR20120049936A (ko) 2012-05-17
US10337140B2 (en) 2019-07-02
KR101891957B1 (ko) 2018-08-28
CN102597361B (zh) 2014-07-16
IL218416A0 (en) 2012-04-30
RU2533134C2 (ru) 2014-11-20

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